JP2017208540A - Plating transfer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plating transfer film with a plating coat formed when preparing a RF circuit board to be used for a RF communication device, and to form a plating coat on a non-conductive substrate with no catalyst activity, such as plastic one by taking advantage of various kinds of transfer techniques using the plating transfer film.SOLUTION: A plating transfer film for RF circuit board preparation is arranged by laminating, on a substrate having release ability, at least a catalyst layer, a plating film and an adhesive layer in turn. The catalyst layer comprises a catalyst composition including (1) composites of metal particles and a dispersant, (2) a solvent and (3) a binder. The metal particles are palladium particles, gold particles, silver particles or platinum particles. The transfer therein refers to in-mold transfer, heat roll transfer or sticker transfer.SELECTED DRAWING: None

Description

  The present invention relates to a plating transfer film.

  There is a technique of decorating the surface of an article using a transfer film in which a picture is incorporated. As a transfer technique for decorating the surface of an article, for example, thermal transfer processing, in-mold transfer processing, and the like are known.

  As an article to be decorated on the surface, there is a non-conductive base material such as plastic. However, non-conductive substrates do not have catalytic activity for electroless plating. Therefore, there is a technique for forming a non-electrolytic plating film by applying a catalytic substance such as metal palladium (Pd) to the non-conductive substrate and then performing electroless plating.

  The present applicant has provided a coating composition for electroless plating capable of forming an electroless plating film on a non-conductive substrate (substrate) (Patent Documents 1 to 3). Further, the present applicant provides a coating composition for performing electroless plating on a non-conductive substrate whose surface has been anionized (Patent Document 4). By these techniques, an electroless plating film excellent in adhesion and appearance film can be formed on a non-conductive substrate.

  The present applicant also provides a transfer technique for attaching a catalyst substance (catalyst composition) to a non-conductive substrate using a transfer film when electroless plating is performed on the non-conductive substrate. (Patent Document 5). By performing electroless plating with this transfer technique, an electroless plating film can be satisfactorily formed on a non-conductive substrate.

  When this transfer film is used, an electroless plating film (catalyst layer) can be satisfactorily formed on the surface of a cylindrical surface such as a cylindrical object from a flat surface such as plastic, A film for electroless plating (catalyst layer) can be formed satisfactorily. According to this technique, an electroless plating film having a smooth surface can be formed on the catalyst layer.

Patent Documents 6 to 8 are techniques for forming a circuit by a resist method on a substrate that can be plated on the entire surface, and then transferring pattern plating by printing. The circuit is integrated in a resin.
Patent Document 6 discloses a technique for manufacturing a multilayer printed wiring board by a resist method on one side or both sides of a conductive substrate. This technique uses an insulating substrate and requires etching of the conductive substrate.
Patent Document 7 discloses a technique for forming a circuit pattern on a support such as a resin tape by a photoresist method. This technique is a technique for transferring only the copper plating layer, and it is necessary to roughen the copper plating layer.

Patent Document 8 discloses a sheet with an electroless plating layer. In this technique, a base layer for electroless plating in which fine particles of metal and metal compound are dispersed in a swellable aqueous resin is formed. The metal compound is present in the base layer for electroless plating, but is reduced by the reducing agent in the electroless plating bath as the electroless plating proceeds.
This technique is also a technique in which the surface of the metal pattern formed on the substrate is soft-etched in order to have smoothness or glossiness.
In Patent Document 9, an ultraviolet curable adhesive is applied, and by irradiating with ultraviolet rays, an electronic component is fixed to a sheet, a resin is molded, and after peeling, a conductive paste such as Ag or Cu is screened. Wiring is done by printing.
In Patent Document 10, an adhesive is applied on a transfer substrate, or an electronic component is positioned and fixed using a double-sided tape or the like, coated with a resin, peeled, and plated (sputtered).
In these techniques, after the parts are transferred, they are connected with a conductive paste and ink.

Patent No.5674561 Patent No. 5428812 Patent No. 5458366 Patent No. 5819020 Patent No. 5843992 JP 63-187695 A Japanese Patent Laid-Open No. 2-122691 JP-A-9-209162 JP 2010-272756 A JP 2001-53413

  An object of this invention is to provide the plating transfer film in which the plating film was formed.

An object of the present invention is to form a plating film on a non-conductive substrate having no catalytic activity, such as plastic, by using various transfer techniques using the plating transfer film.
An object of the present invention is to provide a plating transfer film on which a plating film is formed when a high-frequency circuit board used in a high-frequency communication device is manufactured.

  There is no transfer film in the prior art that can directly form a plating film on a non-conductive substrate.

As a result of intensive studies, the present inventors have developed a plating transfer film, and found that when the plating transfer film is used, the plating film can be directly transferred (formed) to a non-conductive substrate directly. . The plating film transferred by the plating transfer film was a plating film having a smooth surface.
The plating film is preferably a plating film formed by electroless plating or electrolytic plating. The present inventors have found that these techniques lead to an excellent electroless plating technique or electrolytic plating technique.

This invention is the following plating transfer film, the manufacturing method of a plating transfer film, the manufacturing method of plated objects, etc.
First Invention Item 1.
A plating transfer film for creating a high-frequency circuit board in which at least a catalyst layer, a plating film, and an adhesive layer are sequentially laminated on a substrate having releasability,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a catalyst composition containing a solvent and (3) a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. And
The adhesive layer is an acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy adhesive. An adhesive layer comprising at least one adhesive selected from the group consisting of fluororesin, liquid crystal polymer (LCP), polyurethane adhesive, vinyl acetate resin emulsion, EVA resin emulsion and acrylic resin emulsion,
The transfer is in-mold transfer, hot roll transfer or adhesive transfer.
Plating transfer film for creating high-frequency circuit boards.
Item 2.
The dispersant of the catalyst composition is at least selected from the group consisting of a polycarboxylic acid polymer dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and a block copolymer type polymer dispersant having a carboxyl group. Item 2. The plating transfer film according to Item 1, which is one type of dispersant.
Item 3.
The catalyst composition solvent is water; an aprotic polar solvent selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone Polar solvents; alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, 1-butyl alcohol and isobutyl alcohol; ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol and cyclohexanone; ethylene glycol Glycol ethers selected from the group consisting of monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acids selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate Sterols; aromatic hydrocarbons selected from the group consisting of toluene and xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, At least one selected from the group consisting of glycol ether esters selected from the group consisting of butyl cellosolve acetate, methyl carbitol acetate and butyl carbitol acetate; alkanol esters selected from the group consisting of ethyl acetate and butyl acetate; 2-phenoxyethanol Item 3. The plating transfer film according to Item 1 or 2, which is a seed solvent.
Item 4.
The binder of the catalyst composition is an acetal resin, an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin, an imide resin, an amideimide resin, a shellac resin, a melamine resin, a urea resin, a vinyl chloride-vinyl acetate copolymer, and an olefin. Item 4. The plating transfer film according to any one of Items 1 to 3, which is at least one binder selected from the group consisting of resins.
Item 5.
The substrate having releasability is melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin release agent and Item 5. The plating transfer film according to any one of Items 1 to 4, wherein the plating transfer film is a substrate including a release layer made of at least one release agent selected from the group consisting of acrylic resin release agents.
Item 6.
A method for producing a plating transfer film for producing a high-frequency circuit board according to any one of Items 1 to 5,
(1) forming a release layer on the substrate,
(2) A step of applying a catalyst composition to the release layer side of the substrate and providing a catalyst layer;
(3) a step of plating the catalyst layer to form a plating film; and
(4) including a step of providing an adhesive layer on the formed plating film,
Manufacturing method of plating transfer film.
Item 7.
A method for producing a plated article using the plating transfer film for producing a high-frequency circuit board according to any one of Items 1 to 5,
The plating transfer film is formed by laminating at least a catalyst layer, a plating film, and an adhesive layer in order on a substrate having releasability,
(1) a process of attaching an adhesive layer of the plating transfer film to a substrate, and
(2) For the paste obtained by the above step, leaving the catalyst layer of the plating transfer film, the plating film, and the adhesive layer on the substrate, and including the step of peeling the substrate from the substrate,
The steps (1) and (2) are performed by in-mold transfer, hot roll transfer or adhesive transfer.
A method for producing a plated product.

Second invention item 1.
A plating transfer film in which at least a catalyst layer, a plating film, and an adhesive layer or an adhesive layer are sequentially laminated on a substrate having releasability,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a catalyst composition containing a solvent and (3) a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. And
The transfer is in-mold transfer, hot roll transfer or adhesive transfer.
Plating transfer film.

Item 2.
The dispersant of the catalyst composition is at least selected from the group consisting of a polycarboxylic acid polymer dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and a block copolymer type polymer dispersant having a carboxyl group. Item 2. The plating transfer film according to Item 1, which is one type of dispersant.

Item 3.
The catalyst composition solvent is water; an aprotic polar solvent selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone Polar solvents; alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, 1-butyl alcohol and isobutyl alcohol; ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol and cyclohexanone; ethylene glycol Glycol ethers selected from the group consisting of monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acids selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate Sterols; aromatic hydrocarbons selected from the group consisting of toluene and xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, At least one selected from the group consisting of glycol ether esters selected from the group consisting of butyl cellosolve acetate, methyl carbitol acetate and butyl carbitol acetate; alkanol esters selected from the group consisting of ethyl acetate and butyl acetate; 2-phenoxyethanol Item 3. The plating transfer film according to Item 1 or 2, which is a seed solvent.

Item 4.
The binder of the catalyst composition is an acetal resin, an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin, an imide resin, an amideimide resin, a shellac resin, a melamine resin, a urea resin, a vinyl chloride-vinyl acetate copolymer, and an olefin. Item 4. The plating transfer film according to any one of Items 1 to 3, which is at least one binder selected from the group consisting of resins.

Item 5.
The substrate having releasability is melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin release agent and Item 5. The plating transfer film according to any one of Items 1 to 4, wherein the plating transfer film is a substrate including a release layer made of at least one release agent selected from the group consisting of acrylic resin release agents.

Item 6.
The adhesive layer is an acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy adhesive. An adhesive layer made of at least one adhesive selected from the group consisting of polyurethane adhesives, vinyl acetate resin emulsions, EVA resin emulsions and acrylic resin emulsions, or the adhesive layer is an acrylic adhesive Item 1-5, wherein the pressure-sensitive adhesive layer comprises at least one pressure-sensitive adhesive selected from the group consisting of a polystyrene-based adhesive, a polyamide-based adhesive, a silicone-based adhesive, a urethane-based adhesive, and a rubber-based adhesive. The plating transfer film according to any one of the above.

Item 7.
A method for producing the plating transfer film according to any one of Items 1 to 6,
(1) forming a release layer on the substrate,
(2) A step of applying a catalyst composition to the release layer side of the substrate and providing a catalyst layer;
(3) a step of plating the catalyst layer to form a plating film; and
(4) including a step of providing an adhesive layer or an adhesive layer on the formed plating film,
The catalyst layer is formed from a catalyst composition containing (1) a composite of metal particles and a dispersant, (2) a solvent and (3) a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum. Particles,
The transfer is in-mold transfer, hot roll transfer or adhesive transfer.
Manufacturing method of plating transfer film.

Item 8.
A method for producing a plated article using the plating transfer film according to any one of Items 1 to 6,
The plating transfer film is formed by sequentially laminating at least a catalyst layer, a plating film, and an adhesive layer or an adhesive layer on a substrate having releasability, and the catalyst layer includes (1) metal particles and a dispersant. A composite, (2) a solvent and (3) formed from a catalyst composition containing a binder, the metal particles are palladium particles, gold particles, silver particles or platinum particles,
(1) a step of attaching an adhesive layer or an adhesive layer of the plating transfer film to a substrate, and
(2) For the paste obtained in the above step, leaving the catalyst layer of the plating transfer film, the plating film, and the adhesive layer or the adhesive layer on the substrate, including the step of peeling the substrate from the substrate,
The steps (1) and (2) are performed by in-mold transfer, hot roll transfer or adhesive transfer.
A method for producing a plated product.

  Using the plating transfer film of the present invention, a plating film can be satisfactorily formed on the substrate by various transfer techniques.

  Since the plating film is formed on the transfer film, it is possible to form the plating film on the substrate at once by various transfer techniques.

It is the schematic showing the aspect of this invention. It is the schematic showing the aspect of this invention. It is the schematic showing the aspect of this invention. It is the schematic showing the aspect of this invention. It is a result of embodiment (Example 2) of this invention. It is a result of embodiment (Example 10) of this invention. It is a figure which shows the circuit formation method by the metalloid method of this invention. It is a figure which shows the preparation methods of the high frequency double-sided flexible substrate by the metalloid transfer system of this invention. FIG. 3 is a view showing a method 1 for producing a high-frequency substrate by the metal plating transfer system of the present invention. FIG. 4 is a diagram showing a method 2 for producing a high-frequency substrate by the metal plating transfer method of the present invention. It is a figure which shows the board | substrate for high frequency, ML-MTRF. The skin depth for each metal frequency is shown.

  The present invention is described in detail below. However, this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the content of the invention unless otherwise specified.

(1) Description of the Invention In the present invention, a plating film can be satisfactorily formed by various transfer techniques in the technique of plating on a non-conductive substrate having no catalytic activity such as plastic.

  This is because a plating film is formed on a transfer film used in various transfer techniques. The plating film is preferably a plating film formed by electroless plating or electroplating following electroless plating (hereinafter also referred to as “plating”).

For example, a catalyst layer (catalyst composition) such as metal palladium (Pd) is attached to the transfer film to form a catalyst layer, and then plating is performed to form a plating film. Using this plating transfer film, a plating film is satisfactorily formed (transferred) on a non-conductive substrate using various transfer techniques.
An object of the present invention is to provide a plating transfer film on which a plating film is formed when a high-frequency circuit board used in a high-frequency communication device is manufactured.
An object of the present invention is to provide a plating transfer film on which a plating film is formed when a flexible circuit board (FPC) is produced among high-frequency circuit boards.

  In the in-mold transfer method or the hot roll transfer method of the present invention, the adhesive layer (adhesive) of the transfer film is melted by the heat during thermal transfer, and the substrate and the adhesive layer are in close contact (FIGS. 1 to 3).

The present invention uses the transfer film to satisfactorily form a plating film on the surface of a cylindrical surface such as a cylindrical object from a flat surface of plastic or the like, or to form a plating film on a substrate simultaneously with molding in a mold. It can be formed satisfactorily.
For example, it is possible to form (transfer) a plating film on a three-dimensional housing. That is, in addition to the planar material, it is possible to form (transfer) a plating film onto a three-dimensional housing by an in-mold transfer technique.

  In the plating transfer film of the present invention, the plating film itself is formed, and the processes included in the transfer and plating technology can be simplified. When the plating transfer film of the present invention is used, a plating film having a smooth surface can be formed on a non-conductive substrate.

  According to the present invention, in the plating technology, it is not necessary to use an organic solvent at the housing manufacturing site, and an explosion-proof facility or the like is not required. If the plating transfer film has a plating film formed by plating, this plating transfer film is a treatment that does not use harmful hexavalent chromium, and the environmental load is small.

  The plating of the present invention is a general-purpose resin such as acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), polypropylene (PP), acrylic resin, polycarbonate (PC), or a combination of these resins (PC / ABS, etc.). Applicable to plastic products.

  The plating transfer film of the present invention has a plating film formed by pattern plating or partial plating. By transferring (attaching) this plating transfer film onto a substrate (non-conductive substrate, plastic (resin), etc.), a pattern coating or a partially plated plating film can be formed. A molded product (plating object) on which a plating film is placed has excellent adhesion of the plating film.

  The molded product on which the plating film is placed can be used, for example, for automobile parts such as a casing, an emblem, a switch base, a radiator grille, a door handle, and a wheel cover of an electric appliance such as a mobile phone, a personal computer, and a refrigerator. .

  In the plating transfer film of the present invention, the reactivity of plating such as pattern plating is high, and excellent adhesion to chrome plating and excellent smoothness of decorative plating can be expressed on the substrate. In the plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

  When the plating transfer film of the present invention is used, it is not necessary to increase the concentration of the reducing agent in the plating and to increase the reaction temperature of the plating for the purpose of improving the reactivity of the plating. Furthermore, there is no need for an etching step with a harmful substance, a complicated catalyst application step, or the like.

  The mechanism for improving plating reactivity and adhesion is explained (Fig. 4).

The metal particles (Pd particles) having a catalytic action for plating of the catalyst composition (catalyst layer) formed on the transfer film come into contact with the plating solution. As a result of this phenomenon, metal ions in the plating solution are reduced by the metal particles (Pd particles, etc.) deep inside the film from the surface of the catalyst layer (catalyst film), so that the reduced metal takes root. Since it precipitates from the inside of the film, high adhesion between the catalyst layer (catalyst film) and the plating film can be obtained.
Thereby, a plating film appears through the catalyst layer. Thus, when the plating transfer film is attached to the substrate (non-conductive substrate), the catalyst layer and the plating film are transferred (attached), and the plating film appears on the substrate surface. Due to this plating film, conduction occurs to the substrate through the catalyst layer.

  The plating transfer film of the present invention has a high electroless plating reactivity on a transfer film, particularly when a substrate such as ABS (non-conductive substrate, plastic, etc.) is targeted, and can withstand multilayer plating up to plating. Good adhesion can be realized.

  The adhesion mechanism between the base material such as ABS and the catalyst composition (catalyst layer) will be described.

The substrate surface is eroded by the solvent (solvent) component contained in the catalyst composition, and the binder component of the catalyst composition enters the substrate and is mixed with the substrate to form a hybrid layer. Since the butadiene rubber contained in the ABS resin dissolves and swells, the binder component of the catalyst composition enters the substrate.
Since a catalyst layer and a plating film made of the catalyst composition are formed on a base material such as ABS, conduction occurs from the base material such as ABS to the plating film.

Since the surface of the electroless plating base layer of the present invention in the electroless plating layer forming sheet is hydrophilic and swellable, when the electroless plating layer forming sheet is immersed in an electroless plating solution, The plating solution penetrates deep into the underlayer for electroless plating.
Since the electroless plating is performed with the fine metal particles dispersed inside the base layer for electroless plating as a nucleus, the electroless plating layer formed on the surface of the base layer is strong with the base layer. It will be in the state joined to.

  As a result, an electroless plating layer having sufficient strength to proceed with the subsequent processing is formed on the substrate (plastic film support or the like). In the present invention, since the plating catalyst layer is also conductive and the smoothness of the substrate is transferred, it is not necessary to subject the surface to a soft etching treatment.

  Since the plating film is formed on the plating transfer film of the present invention, it is possible to form the plating film on the substrate at once by various transfer techniques.

  Since the plating transfer film of the present invention can form a plating film with excellent thickness uniformity, when the plating film is formed on an article substrate (substrate) using this plating transfer film, the article substrate A plating film having excellent thickness uniformity can be formed on the (substrate).

By using the plating transfer film of the present invention, it is possible to easily transfer a conductive circuit to a substrate that cannot normally withstand a plating bath or a substrate that is not suitable for a plating bath by various transfer techniques. .
The present invention provides a plating transfer film on which a plating film is formed when a high-frequency circuit board used in a high-frequency communication device, particularly a flexible circuit board (Flexible Printed Circuits: FPC), is produced. Excellent to provide.
FPC is flexible and can be repeatedly deformed with a weak force, and maintains the electrical characteristics even when deformed.
When the circuit board is produced, by using the plating transfer film on which the plating film of the present invention is formed, a resist becomes unnecessary, and the copper waste liquid can be eliminated. Moreover, it is also possible to produce a thin film circuit by using the plating transfer film of the present invention.
By using the plating transfer film of the present invention, a high-frequency laminated flexible substrate can be produced.

(2) Transfer Technology FIGS. 1 to 3 show schematic views of embodiments of the present invention.

  A transfer technique using the plating transfer film of the present invention will be described.

  The plating transfer film of the present invention is formed by laminating at least a catalyst layer, a plating film, and an adhesive layer or an adhesive layer in order on a substrate having releasability, and the catalyst layer comprises (1) metal particles and a dispersant. And (2) a solvent and (3) a catalyst composition containing a binder, wherein the metal particles are palladium particles, gold particles, silver particles or platinum particles.

  By the transfer technique using the plating transfer film of the present invention, a plating film (electroless plating or the like) can be attached to a non-conductive substrate (substrate, molded product), and the non-conductive substrate can be decorated. In particular, in the manufacture of printed wiring boards for electronic equipment, metal wiring circuits (high-frequency circuit boards and flexible circuit boards (FPCs) used in high-frequency communication devices) are formed by the transfer technology using the plating transfer film of the present invention. Can do.

  The transfer technique of the present invention is mainly a hot roll transfer technique, an in-mold transfer technique, or an adhesive transfer.

Thermal roll transfer technology (Figures 1 and 3)
By applying the plating transfer film of the present invention to the hot roll transfer technology, a pattern, metallic tone, pearl, etc., from the plane of a non-conductive substrate (molded product) such as plastic to the surface of a cubic surface such as a cylindrical object. Further, a design (plating) such as a matte tone can be imparted (decorated). The hot roll transfer technology is a decoration method with less environmental impact due to organic solvents, compared to technologies such as printing and painting on molded products.

In-mold transfer technology (Figures 2 and 3)
By applying the plating transfer film of the present invention to the in-mold transfer technology, a non-conductive substrate such as plastic (which becomes a base) is molded in a mold, and at the same time, a molded product having a cubic curved surface. Various highly designable designs (plating) can be applied (decorated) on the surface with a high degree of positional accuracy on the surface of the cubic curved surface. The in-mold transfer technique is a decoration method with less environmental burden due to organic solvents compared to techniques such as printing and painting for molded products, and can save space and cost.

Adhesive transfer technology (Figure 3)
By applying the plating transfer film of the present invention to the pressure sensitive adhesive transfer technology, a pattern, metal tone, etc. can be applied from the plane of a non-conductive substrate such as plastic (substrate, molded product) to the surface of a cubic surface such as a cylinder. Design (plating) such as pearl and matte can be imparted (decorated). Compared to printing, painting, and other technologies for molded products, the adhesive transfer technology is a decorative method with less environmental impact due to organic solvents.

(3) Plating transfer film The plating transfer film of the present invention has at least a catalyst layer and a plating film (electroless plating or electroless plating following electroless plating (hereinafter, collectively referred to as “plating”) on a substrate having releasability. A plating film formed by the above), and an adhesive layer or an adhesive layer are sequentially laminated,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a catalyst composition containing a solvent and (3) a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. And
The transfer is in-mold transfer, hot roll transfer, or adhesive transfer.

  The plating transfer film of the present invention can be applied to a transfer technique for decorating a non-conductive substrate (molded product). Using the plating transfer film of the present invention, a plating film can be formed (exposed) on a non-conductive substrate (molded product).

  In the production of a printed wiring board of an electronic device, a metal wiring circuit (a high-frequency circuit board or a flexible circuit board (FPC) used in a high-frequency communication device) can be formed using the plating transfer film of the present invention.

(3-1) The substrate plating transfer film having releasability has a substrate.

  Conventionally known materials can be used as the material of the substrate (substrate sheet). For example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT); polypropylene (PP), polycarbonate (PC), polyethylene (PE), polystyrene (PS), polyvinyl alcohol (PVA) It is preferable to use a substrate using a resin film such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide (PA, nylon), polyimide (PI), cellulose acetate, or ionomer.

  Further, it is preferable to use paper such as condenser paper or paraffin paper, or a sheet such as nonwoven fabric.

  These can be used singly or can be arbitrarily combined. Among these, polyethylene terephthalate (PET), which is a versatile plastic that can be thinned and is inexpensive, is preferable.

The thickness of the substrate can be appropriately adjusted according to the transfer mode of the plating transfer film. About 10 to 60 μm is preferable because the strength of the plating transfer film can be maintained and the shape followability to the substrate (non-conductive substrate) is good and the catalyst layer and plating film can be transferred well. About 15-50 μm is more preferable, and about 20-40 μm is even more preferable.
For example, PET having a thickness of about 38 μm is generally preferable in terms of handling, cost, and the like.

  The substrate having releasability can impart releasability to the substrate by including a release layer exhibiting releasability.

In the method for producing an electroless plated product using the plating transfer film of the present invention, the release layer is affixed to the substrate with the adhesive layer of the plating transfer film by a transfer technique such as hot roll transfer or in-mold transfer, It is a boundary layer when the catalyst layer, the plating film, and the adhesive layer of the plating transfer film are left on the substrate, and the substrate and the release layer are peeled from the substrate, with respect to the obtained paste.
The release layer is a layer for easily peeling the base material (base material sheet) from the catalyst layer in a state where the adhesive layer and the catalyst layer are attached to the substrate. The release layer remains on the substrate side when the substrate is peeled off.

  By providing a release layer, the catalyst layer can be reliably and easily transferred from the plating transfer film of the present invention to the substrate (non-conductive substrate), and the substrate and the release from the substrate on which the catalyst layer and the plating film are attached. The base material part which has a layer can be peeled reliably.

As release agents used in the release layer, melamine resin release agents, silicone release agents, fluororesin release agents, cellulose resin release agents, urea resin release agents, polyolefin resin release agents, paraffin release agents, acrylics It is preferable to use a resin-based release agent or the like.
These can be used singly or can be combined release agents arbitrarily combined. Among these, it is more preferable to use a melamine resin release agent, a silicone release agent, or the like.

In order to form a release layer on a substrate, it is preferable to use a release composition prepared by dissolving or dispersing an additive necessary for the release agent in an appropriate solvent. The release layer can further contain a resin, an additive, and the like. The resin used for forming the release layer is preferably formed using a thermoplastic resin.
For example, it is preferable to use an acrylic resin, a polyester resin, a cellulose derivative resin, a polyvinyl acetal resin, a polyvinyl butyral resin, a vinyl chloride-vinyl acetate copolymer, a chlorinated polyolefin resin, or the like.

  The release composition is applied and dried on a substrate by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, a gravure reverse roll coating method, and then released. A layer can be formed.

  The thickness of the release layer is preferably about 0.1 to 5 μm, more preferably about 0.2 to 3 μm.

(3-2) Catalyst layer plating transfer film has a catalyst layer.

  The catalyst layer is composed of (1) a composite of metal particles and a dispersant (metal composite), (2) a catalyst composition containing a solvent and (3) a binder, and the metal particles include palladium particles, gold particles, It is characterized by being silver particles or platinum particles.

(3-2-1) Composition of catalyst composition
Composite of metal particles and dispersant (1)
The catalyst composition includes a composite of metal particles and a dispersant.

  As the complex, a palladium complex (Pd complex) containing palladium particles (Pd particles) is preferable. For example, Pd composites can be prepared from palladium ions (Pd ions) supplied from palladium compounds (Pd compounds) such as palladium chloride (Pd chloride) in the presence of dispersants such as polycarboxylic acid polymers, hydrazine hydrates, etc. Can be obtained by reduction with a secondary or tertiary amine.

Dispersant As the dispersant, it is preferable to use a polycarboxylic acid dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group, and the like. A commercial item can also be used for a dispersing agent.

As the polycarboxylic acid polymer dispersant, it is preferable to use polycarboxylic acid ammonium salt, polycarboxylic acid sodium salt, polycarboxylic acid triethylamine salt, polycarboxylic acid triethanolamine salt or the like.
For example, Nopco Santo K, R, RFA, Nop Cospers 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, 5468 manufactured by San Nopco Co., Ltd. 532A etc. can be used.

  As the block copolymer type polymer dispersant having a hydroxyl group, polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether carboxylate or the like is preferably used. For example, DISPERBYK190, 2010 manufactured by Big Chemie Japan Co., Ltd. can be used.

  As the block copolymer type polymer dispersant having a carboxyl group, an acrylic acid-maleic acid copolymer, a styrene-maleic acid copolymer, an acrylic acid-sulfonic acid copolymer, or the like is preferably used. For example, Big Chemie Japan Co., Ltd. DISPERBYK180, 187, 191, 194, Nippon Shokubai Aquaric TL, GL, LS can be used.

  A dispersing agent can be used 1 type or in combination of 2 or more types. Among the dispersants, a block copolymer type polymer dispersant having a carboxyl group is preferable.

Metal particles Metal particles function as an electroless plating catalyst. Ultra fine particles of noble metals such as palladium particles (Pd particles), gold particles (Au particles), silver particles (Ag particles), platinum particles (Pt particles), etc. It is. Pd particles are particularly preferable as the metal particles.

Pd particles
Pd particles can be obtained by reducing Pd ions supplied from a Pd compound using a reducing agent in the presence of a dispersant (liquid phase reduction method).

  As a Pd compound that supplies Pd ions, palladium chloride (Pd chloride), palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate, etc. are used. It is preferable.

  Pd compounds can be used alone or in combination of two or more.

  As a reducing agent, primary, secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine, diethanolamine, triethanolamine, ascorbic acid, 2, It is preferable to use enediols such as 3-dihydroxymaleic acid.

Examples of the reducing agent include hydroxylamine compounds such as N, N-dialkylhydroxylamine; hydrazine compounds such as N, N-dialkylhydrazine; phenols such as hydroquinone and aminophenol; and phenylenediamines; 2-hydroxy It is preferable to use hydroxyketones such as acetone, 2-hydroxyhexane-1,3-dione, citric acid, malic acid, and hydroxycarboxylic acids;
As reducing agents, enediols such as ascorbic acid and 2,3-dihydroxymaleic acid; aminoalcohols such as diethanolamine, triethanolamine and N, N-dimethylethanolamine; primary amines, secondary amines, It is preferable to use various amines such as tertiary amines.

  The following (2) solvent can be used for the solvent (solvent for making a dispersing agent and Pd ion exist) used in the reduction. A solvent can be used 1 type or in combination of 2 or more types.

  Examples of the method for reducing Pd ions include a method in which a dispersing agent and Pd ions are present in a solvent and then the reducing agent is added to the solvent. Thereby, Pd ion and a reducing agent contact and it can reduce Pd ion.

  Most of the Pd particles are considered to be attached to the outside of the dispersant. For example, when the shape of the Pd composite (the shape of the entire dispersant) is a dense sphere, it is considered that most of the Pd particles are attached to the spherical surface side (outside).

  The weight ratio of the Pd particles to the dispersant in the Pd composite is preferably about Pd particles: dispersant = 50: 50 to 95: 5, more preferably about Pd particles: dispersant = 65: 35 to 85:15. .

For example, Pd chloride (about 1 part by weight) is dissolved in purified water (about 89 parts by weight), and trisodium citrate (about 10 parts by weight) is further dissolved and stirred uniformly. Subsequently, sodium borohydride (about 0.01 part by weight) is added to reduce the salt Pd, whereby a palladium colloid stabilized with citric acid and converted into a protective colloid (Pd colloid) can be obtained.
Thereafter, concentration desalting is performed by ultrafiltration to obtain a Pd colloid containing Pd (about 0.5 parts by weight).

  The average particle diameter of the Pd particles alone is not particularly limited, and is preferably about 2 to 10 nm. The particle diameter of the Pd particles can be measured using a transmission electron microscope. The average particle size of the Pd particles can be calculated by randomly selecting 10 Pd particles, measuring the particle size of the Pd particles with a transmission electron microscope, and averaging the number (number-based average diameter). ).

  The average particle size of the Pd composite is not particularly limited, and preferably has a spherical structure with an average particle size of about 20 to 300 nm as a whole. The average particle diameter of the Pd composite can be measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average diameter).

Other metal particles Other metal particles that function as an electroless plating catalyst are preferable. Metal particles produced by a plasma method in a microwave liquid, metal particles produced by an ultrasonic method, gas phase method (CVD laser) Etc.) and noble metal-supported fine particles are preferred. These metal particles are preferably noble metal ultrafine particles such as Pd particles, Au particles, Ag particles, and Pt particles.

  When the metal particles are Pt particles, platinum ions (Pt ions) supplied from platinum compounds (Pt compounds, noble metal compounds) such as platinum chloride (IV) in the presence of a dispersant are converted to secondary grades such as hydrazine hydrate. Alternatively, it can be obtained by reduction with a tertiary amine. The composite is preferably obtained by reducing Pt ions in the presence of a dispersant.

  As Pt compounds (noble metal compounds) that supply Pt ions, platinum chloride (II), platinum chloride (IV), hexachloride platinum (IV) acid, tetrachloride platinum (II) acid, potassium hexachloride platinum (IV) acid, Potassium tetrachloride platinum (II), ammonium hexachloride platinum (IV), platinum (IV) oxide, platinum (II) bromide, platinum (IV) bromide, platinum (II) hydroxide, platinum fluoride (VI Etc.) are preferred.

  Other conditions are the same as in the case of the Pd particles.

  Pd particles are particularly preferable as the metal particles.

Solvent (2)
The catalyst composition includes a solvent.

  The solvent (dispersion medium) can disperse the metal complex (Pd complex or the like). Moreover, the solvent is excellent in affinity with the binder.

  The solvent is determined by considering the (1) dispersibility of the composite of metal particles and dispersant (metal composite) contained in the catalyst composition, and (3) the solubility of the binder, and further the viscosity and evaporation of the catalyst composition. It is preferable to select from the viewpoint of speed or the like. Moreover, it is preferable to satisfy the point that the catalyst composition is in good contact with a non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)) through the adhesive layer.

Solvents include alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diacetone alcohol (4-hydroxy-4-methyl) It is preferable to use (additionally) ketones such as -2-pentanone) and cyclohexanone;
As solvents, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate; aromatic hydrocarbons such as toluene and xylene; n- It is preferable to use (additionally) aliphatic hydrocarbons such as hexane, n-heptane and mineral spirits;
As solvents, glycol ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, and butyl carbitol acetate; alkanol esters such as ethyl acetate and butyl acetate; 2-phenoxyethanol (ethylene glycol phenyl ether) Etc. (additional) are preferably used.

In particular, it is preferable to use a solvent having a low evaporation rate in consideration of printability and paintability, and a leveling process after printing and painting.
Examples of the solvent having a low evaporation rate include diacetone alcohol, cyclohexanone, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, and 2-phenoxyethanol. These solvents are preferably used.

  From the viewpoint that the metal complex (Pd complex etc.) in the catalyst composition can be dispersed well, at least one selected from the group consisting of water and an aprotic polar solvent such as N-methylpyrrolidone is preferable.

  As aprotic polar solvents, aprotic polar solvents such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc); dimethyl sulfoxide; γ-butyrolactone, etc. It is preferable to use it. Of the aprotic polar solvents, at least one selected from the group consisting of NMP, DMF and DMAc is more preferable.

  The solvent can be converted after the reduction reaction of metal ions (such as Pd ions). For example, the solvent can be converted from water to NMP.

  A solvent can be used 1 type or in combination of 2 or more types.

The content of the dispersion solvent in the catalyst composition (the total amount when two or more solvents are used) is not particularly limited, and is 1 × 10 4 with respect to 100 parts by weight of the metal composite (Pd composite etc.). ^{About 2} to 1 × 10 ⁶ parts by weight is preferable. The metal complex (Pd complex or the like) is preferably contained in about 1% by weight in the dispersion solvent.
The dispersion solvent is more preferably about 5 × 10 ^{2 to} 3 × 10 ⁵ parts by weight, and about 1 × 10 ³ to 2 × 10 ⁵ parts by weight with respect to 100 parts by weight of the metal composite (Pd composite etc.) More preferred is about 5 × 10 ³ to 2 × 10 ⁴ parts by weight.

Binder (3)
The catalyst composition includes a binder.

  Binder is good from the viewpoint of viscosity of catalyst composition, adhesion between catalyst composition and non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)), curing conditions, etc. It is preferable to select a material that can obtain electroless plating reactivity. The binder is dispersed or dissolved in the solvent.

  Specifically, acetal resin (POM), epoxy resin, ester resin, acrylic resin, urethane resin, amide resin (PA, polyamide, nylon), imide resin (polyimide), amideimide resin (PAI, polyamideimide), shellac resin It is preferable to use melamine resin, urea resin, vinyl chloride-vinyl acetate copolymer (vinyl chloride / vinyl acetate modified resin), olefin resin (polyolefin) and the like.

  The vinyl chloride-vinyl acetate copolymer (vinyl chloride / vinyl acetate modified resin) is a copolymer resin of vinyl chloride and vinyl acetate.

As the acetal resin (POM), polyvinyl acetal or the like is preferably used. Polyvinyl acetal is a resin obtained by acetalizing polyvinyl alcohol with an aldehyde.
Polyvinyl formal is obtained by acetalization using formalin (formaldehyde 37% aqueous solution) as an aldehyde. Acetalized with butanol (butyl alcohol) as an aldehyde is polyvinyl butyral (butyral resin, PVB).

As the amide resin, nylon 6 (ε-caprolactam), nylon 11 (undecane lactam), nylon 12 (lauryl lactam) or the like is preferably used.
Amide resin is nylon 66 (hexamethylenediamine + adipic acid), nylon 610 (hexamethylenediamine + sebacic acid), nylon 6T (hexamethylenediamine + terephthalic acid), nylon 6I (hexamethylenediamine + isophthalic acid), nylon 9T It is preferable to use (nonanediamine + terephthalic acid), nylon M5T (methylpentadiamine + terephthalic acid), nylon 612 (co-condensation polymer of ω-amino acids of caprolactam and lauryl lactam), and the like.

  The amidoimide resin is a resin in which an amide bond is introduced into the polyimide main chain, and it is preferable to use a resin obtained by a reaction between trimellitic anhydride and diisocyanate, a reaction between trimellitic anhydride chloride and diamine, or the like.

  It is preferable to use an epoxy resin. By using an epoxy resin, an electroless plating coating film can be more firmly adhered to an article containing an ABS resin or the like. The epoxy resin becomes a polymer base material (matrix resin) constituting the coating film for electroless plating.

  As the epoxy resin, either a one-component or two-component epoxy resin can be used. Epoxy resins include modified epoxy resins.

  As the one-component epoxy resin, it is preferable to use bisphenol A type, bisphenol F type, novolak type, phenol novolak type, cresol novolak type, glycidyl ester type, glycidyl ether type, biphenyl type and the like.

  Examples of the one-component epoxy resin include EPICLON830, 830-S, 835, 840, 840-S, 850, 850-S, N-730A, N-740A, N-770, and N-775 manufactured by DIC Corporation; Nagase ChemteX Corporation XNR-3053, XNR3505, XN1244, XN1278; Arakawa Chemical Industries Arakid 9201N, 9203N, 9205, 9208, Modix 301,302,401; Toagosei Co., Ltd. Aron Mighty AP-0786, AS- Commercially available products such as 60, BX-60, AS-315 can be used.

  As the two-component epoxy resin, a resin containing the above epoxy resin as a main agent can be used. As the curing agent used with this agent, it is preferable to use polyamide, polyamine, polyamidoamine, ketimine, imidazole, diamine, diaminediamide, tetrahydrophthalic anhydride and the like.

  The two-part epoxy resin is, for example, jER-806, 807, 825, 827, 828, 1256, 4250, 4275, W2821R70 manufactured by Mitsubishi Chemical Corporation; Adeka Resin EP-4100HF, EP- manufactured by ADEKA Corporation Commercially available products such as 4088S, EPR-4030; AV138-HV998, XNR3106-XNH3103 manufactured by Nagase ChemteX Corporation; Aronmite AP-400BD manufactured by Toagosei Co., Ltd. can be used.

  Examples of the curing agent for the two-component epoxy resin include lacamide 17-202, TD-961, TD-977, TD-992, WN-155, WN-170, WN-405, and WN-505 manufactured by DIC Corporation; Mitsubishi Chemical Corporation jER Cure-ST11, ST12, St13, ST14, LV11, DC11, RC11, FL11, QX11, H3, WD11M60; ADEKA Adeka Hardener EH-3636AS, EH-5010S, EH-5015S; Commercial products such as Hitachi Chemical Co., Ltd. HN-2200, HN-2000, HN-5500; T & K TOKA Co., Ltd. tomide 245, 275, 210, 241, Fuji Cure-5000, FXS-654, FXS-8077 Can be used.

  The epoxy resin is preferably a one-component epoxy resin from the viewpoints of workability, stability over time, and the like. Epoxy resins can be used alone or in combination of two or more.

  The curing temperature of the epoxy resin is preferably 60 to 200 ° C, more preferably 80 to 150 ° C.

As the amide resin, nylon 6 (ε-caprolactam), nylon 11 (undecane lactam), nylon 12 (lauryl lactam) or the like is preferably used.
Amide resin is nylon 66 (hexamethylenediamine + adipic acid), nylon 610 (hexamethylenediamine + sebacic acid), nylon 6T (hexamethylenediamine + terephthalic acid), nylon 6I (hexamethylenediamine + isophthalic acid), nylon 9T It is preferable to use (nonanediamine + terephthalic acid), nylon M5T (methylpentadiamine + terephthalic acid), nylon 612 (co-condensation polymer of ω-amino acids of caprolactam and lauryl lactam), and the like.

  The amidoimide resin is a resin in which an amide bond is introduced into the polyimide main chain, and it is preferable to use a resin obtained by a reaction between trimellitic anhydride and diisocyanate, a reaction between trimellitic anhydride chloride and diamine, or the like.

  The acrylic resin is a polymer of an acrylate ester or a polymer of a methacrylic ester or a copolymer using these as a comonomer, for example, a polymethyl methacrylate resin, a polymethyl acrylate resin, an ethylene-methyl acrylate copolymer. It is preferable to use ethylene-methyl methacrylate copolymer.

  The binder is selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, amide resin, imide resin, amideimide resin, shellac resin, melamine resin, urea resin, PVC-vinyl acetate copolymer and olefin resin. At least one selected is preferred. Two or more binders can be used in combination.

The content of the binder is preferably about 1 to 1 × 10 ⁵ parts by weight and more preferably about 50 to 5 × 10 ⁴ parts by weight with respect to 100 parts by weight of the metal composite (Pd composite or the like).

  The binder preferably has a solid content ratio of about 1 to 50% by weight.

(3-2-2) Production method of catalyst composition As described above, metal particles (Pd particles, etc.) are supplied from metal compounds (Pd compounds, etc.) in the presence of a dispersant. Can be obtained by reducing with a reducing agent.

The catalyst composition is
(i) (2) A metal ion (Pd ion, etc.) and a dispersant are present in a solvent, and the metal ion (Pd ion, etc.) is reduced using a reducing agent. (1) Metal particles (Pd particles) Etc.) and a composite of a dispersant,
(ii) (2) in a solvent, (3) a step of mixing a binder to produce a mixture, and
(iii) The mixture of the complex of (2) the solvent and (1) metal particles (Pd particles, etc.) obtained in the step (i) and the dispersant was obtained in the step (ii) (2) Mixing a solvent and (3) a mixture of binders;
It is preferable to manufacture by the manufacturing method containing this.

  Either step (i) or step (ii) may be the previous step.

  According to the said manufacturing method, the catalyst composition applicable to the plating transfer film utilized with a transfer technique can be manufactured.

  Using this plating transfer film, a catalyst layer (catalyst composition) and a plating film can be formed (exposed) on a non-conductive substrate.

  The catalyst composition of the present invention is highly reactive in plating (electroless plating or electrolytic plating), has good adhesion to plating, and can form a plating film that can exhibit good smoothness. .

  With the plating transfer film, it is possible to form a partial plating while suppressing the spread of the pattern on a non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)). When a plating transfer film is used, an etching process using a harmful substance, a complicated catalyst application process, and the like are not required.

Process (i)
(2) A metal ion (Pd ion, etc.) and a dispersant are present in a solvent, and the Pd ion is reduced using a reducing agent. (1) A complex of metal particles (Pd particles) and a dispersant. Is made.

  First, a metal ion (Pd ion or the like) and a dispersant are present in a solvent (dispersion medium). As a metal ion (Pd ion or the like), a metal compound (Pd compound or the like) that supplies the metal ion (Pd ion) as a supply source can be used.

  Use amount (parts by weight) of each component is based on “metal compound (Pd compound, etc.)”.

  As the dispersant, the dispersant can be used. The use ratio (weight ratio) between the metal ions (Pd ions, etc.) and the dispersant is preferably about 10-200 parts by weight of the dispersant with respect to 100 parts by weight of the metal compound (Pd compound, etc.), 30 About 150 parts by weight is more preferable, and about 50-100 parts by weight is even more preferable.

As the solvent, the solvent (2) can be used. The amount of the solvent used is not particularly limited as long as the metal ions (Pd ions, etc.) and the dispersant can be uniformly present, and 1 × 10 ^{4 to} 3 × with respect to 100 parts by weight of the metal compound (Pd compound, etc.). About 10 ⁵ parts by weight is preferable, and about 1 × 10 ⁴ to 1 × 10 ⁵ parts by weight is more preferable.

Next, a metal ion (Pd ion or the like) is reduced by the reducing agent by reacting the metal ion (Pd ion or the like) with a reducing agent. That is, a reduction reaction of metal ions (Pd ions, etc.) occurs, and as a result, a complex (metal complex (Pd complex, etc.)) of the metal particles (Pd particles, etc.) and the dispersant can be obtained. it can.
As the reducing agent, a reducing agent used for producing the metal complex (Pd complex or the like) can be used. The amount of the reducing agent to be used is not particularly limited, and is preferably about 100 to 800 parts by weight, more preferably about 200 to 600 parts by weight with respect to 100 parts by weight of the metal compound (Pd compound or the like).

  The reaction using the reducing agent is preferably carried out at a temperature of about 35 to 45 ° C, and preferably raised to about 50 to 60 ° C. The reaction time is not particularly limited, and is preferably about 1 to 5 hours.

  The pressure and atmosphere during the reaction are not particularly limited, and the reaction is preferably performed under atmospheric pressure or air (air) atmosphere. The reaction can be carried out in an open system such as a beaker. As a reaction method, it is preferable to stir a solution containing a metal ion (Pd ion or the like) (metal compound (Pd compound or the like)), a dispersant and a reducing agent with a bladed stirring rod.

A mixture containing a complex of a solvent and metal particles (Pd particles, etc.) and a dispersant (metal complex-containing liquid (Pd complex-containing liquid, etc.)) is ultrafiltered to obtain metal particles (Pd particles, etc.) and a dispersant. It is preferable to separate the complex.
By this operation, it is possible to remove inorganic salts, excess dispersants, and the like contained in the metal complex-containing liquid (Pd complex-containing liquid and the like). For example, the Pd complex-containing liquid can be filtered to make up for the dispersion solvent. This process can be repeated.

  It is possible to convert the solvent after the reduction reaction of metal ions (Pd ions, etc.). For example, by using water as the solvent and then converting the water to NMP or the like (solvent, dispersion medium), NMP ((2) solvent) and (1) metal particles (Pd particles etc.) and a dispersing agent It is possible to make a mixture of

Step (ii)
(2) A mixture is prepared by mixing (3) a binder in a solvent.

  As the solvent, (2) solvent such as 2-phenoxyethanol, diacetone alcohol, methyl isobutyl ketone, cyclohexanone and the like can be used. The amount of solvent used is not particularly limited.

  As the binder, the above (3) binder can be used. It is preferable that the amount of the binder used considers the viscosity of the catalyst composition. Moreover, it is preferable to consider the adhesiveness between the catalyst composition and the non-conductive substrate (ABS resin, glass plate, etc.), curing conditions, and the like via the adhesive layer.

  The mixing is not particularly limited, and it is preferable to perform the mixing under an atmospheric pressure or an air (air) atmosphere. Mixing can be performed in an open system such as a beaker. As a mixing method, it is preferable to stir the mixture containing the solvent and the binder with a bladed stirring rod.

Step (iii)
(2) The solvent obtained in the step (ii) and the mixture of the complex of (2) the solvent obtained in the step (i) and (1) the metal particles (Pd particles, etc.) and the dispersant, 3) Mix the binder mixture.

(3-2-3) Formation of catalyst layer In the method for producing a plated product using the plating transfer film of the present invention, the catalyst layer is formed of the plating transfer film by a transfer technique such as hot roll transfer or in-mold transfer. Adhering the adhesive layer to the substrate (non-conductive substrate), then leaving the catalyst layer of the plating transfer film, the plating film and the adhesive layer on the substrate, and leaving the substrate and the substrate from the substrate This is a layer provided on the substrate (non-conductive substrate) after peeling the release layer.

  The catalyst layer is a layer for performing plating by being provided on the substrate via an adhesive layer. The catalyst layer remains on the substrate side when the substrate is peeled off.

  The catalyst composition for forming the catalyst layer is formed on the substrate-peeling layer by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, a gravure reverse roll coating method, The catalyst layer can be formed by coating and drying.

The thickness of the catalyst layer is preferably about 0.01 to 10 μm, more preferably about 0.02 to 8 μm, and more preferably about 0.03 to 5 μm because electroless plating can be satisfactorily performed and a plating film can be satisfactorily formed on the substrate. A thickness of about 0.05 μm (50 nm) to 2 μm is particularly preferable.
By applying plating (electrolytic plating following electroless plating or electroless plating) to the catalyst layer and using the resulting plating transfer film, the intended design can be expressed on the substrate.

(3-3) Plating film The plating transfer film has a plating film. The plating film is formed by electroless plating or electroplating following electroless plating (hereinafter also referred to as “plating”).

In the method for producing a plated product using the plating transfer film of the present invention, the plating film is formed by applying the adhesive layer of the plating transfer film to a substrate (non-conductive substrate) by a transfer technique such as hot roll transfer or in-mold transfer. Paste to.
Next, after leaving the catalyst layer, the plating film and the adhesive layer of the plating transfer film on the substrate, and peeling the substrate and the release layer from the substrate, the substrate (non-conductive substrate) is obtained. It is a layer provided in.

The plating film remains on the substrate side when the substrate is peeled off. Plating (electroless plating or electrolytic plating) is performed on the catalyst layer of the plating transfer film. After the plating transfer film is transferred to the substrate (non-conductive substrate), the plating film can be exposed.
Design properties can be imparted to the substrate (molded product or molded product). It is a layer for expressing patterns, characters, pattern-like patterns, etc. on the substrate. For example, wood, stone, cloth, sand, geometric patterns, characters, stripes, gradation patterns and the like can be given to the substrate.

  The thickness of the plating film is preferably about 0.05 to 10 μm, more preferably about 0.1 to 6 μm, and still more preferably about 0.2 to 4 μm, because it can give a good design to the substrate in the case of decorative use. A thickness of about 0.3 to 2 μm is particularly preferable. The target design can be expressed on the substrate by plating.

  Moreover, what is necessary is just to set it as the thickness suitable for the objective use suitably by the electric current and voltage which are requested | required in the case of an electronic circuit use. A method for producing a plating film on the plating transfer film will be described later.

(3-4) Adhesive layer The plating transfer film has an adhesive layer.

  In the method for producing a plated product using the plating transfer film of the present invention, the adhesive layer is formed by using a transfer technology such as hot roll transfer or in-mold transfer to form a base (non-conductive substrate) of the plating transfer film. This is a layer for adhering the substrate and the catalyst layer to each other when the substrate is attached. The adhesive layer exists between the substrate and the catalyst layer.

  The adhesive layer remains on the substrate side when the substrate is peeled off. Due to the adhesive layer, the catalyst layer can be satisfactorily formed on the substrate, and thereafter electroless plating can be satisfactorily performed.

Adhesive layer is acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy adhesive, Fluorine resin (fluorine resin adhesive), liquid crystal polymer (Liquid Crystal Polymer or Liquid Crystal Plastic, LCP) (LCP adhesive), polyurethane adhesive, vinyl acetate resin emulsion, EVA resin emulsion, acrylic resin emulsion It is preferable to use an adhesive composition containing an adhesive (resin) such as
These can be used alone or can be arbitrarily combined into a resin composition.

  The adhesive layer is preferably selected in consideration of compatibility with the binder contained in the catalyst composition and adhesion to the substrate. For example, it is more preferable to use an acrylic resin or the like.

  This adhesive composition is applied onto the substrate-release layer-catalyst layer by a known means such as gravure coating method, roll coating method, comma coating method, gravure printing method, screen printing method, gravure reverse roll coating method, etc. -It can be dried to form an adhesive layer.

  The thickness of the adhesive layer is preferably about 0.1 to 5 μm, and more preferably about 1 to 5 μm because the catalyst layer can be formed (adhered) well on the substrate.

  The adhesive is generally cured after solvent drying at room temperature (has thermosetting properties) (room temperature adhesive). When designing with a room temperature adhesive, the reaction proceeds at room temperature, so it is possible to limit the time and temperature until the transfer film is transferred. Moreover, since it hardens | cures at normal temperature, it is possible to suppress stickiness (it does not generate | occur | produce) when transferring a transfer film.

High frequency circuit board
The present invention relates to a high-frequency circuit board used in a high-frequency communication device.
In recent years, with an increase in the amount of information communication, for example, in devices such as IC cards and mobile phones, communication in a higher frequency region such as microwaves and millimeter waves has become popular. Therefore, there is a need for a high-frequency circuit board that can be used in a high-frequency region and has a smaller transmission delay and transmission loss.
The transmission speed V related to the transmission delay and the transmission loss αd can be expressed as (Equation 1) and (Equation 2) below using the relative dielectric constant εr and the dielectric loss tangent tanδ of the substrate material.
V∝1 / √εr ... (Formula 1)
αd∝f × √εr × tanδ ... (Formula 2)
(F: frequency)
From (Equation 1), in order to reduce the transmission delay, that is, increase the transmission speed V, it is preferable to use a material having a low relative dielectric constant εr (low relative dielectric constant). Further, from (Equation 2), in order to reduce the transmission loss αd, it is preferable that the relative dielectric constant εr and the dielectric loss tangent tanδ are small.
Epoxy adhesives Epoxy adhesives should be stored at low temperatures (refrigerators, etc.) (half-life) and hot-pressed during processing. Epoxy resin can be used as an insulating material for circuit laminates.
Epoxy adhesives are advantageous when manufacturing high-frequency circuit boards.
It is preferable to use an epoxy resin adhesive, an acrylic resin adhesive, or the like as an adhesive layer when a flexible circuit board (FPC) is manufactured.

  Epoxy adhesives are thermosetting adhesives that are generally cured by a thermal process.

In transfer techniques such as hot roll transfer and in-mold transfer, it is preferable to use an adhesive. For production of an electronic circuit board, it is preferable to use an epoxy-based adhesive bonded with a hot roll, a hot press or the like.
As an epoxy-based adhesive, Admixma NC0209 manufactured by NAMICS, ABF film GZ41 manufactured by Ajinomoto Technofine, or the like can be used.
Fluororesin (Fluororesin adhesive)
A fluororesin such as polytetrafluoroethylene (PTFE) is a material having a low relative dielectric constant and a low dielectric loss tangent, and is preferable as a dielectric layer of a high-frequency circuit board. However, the fluororesin has a remarkably low surface energy and is non-adhesive. Therefore, it is preferable to ensure sufficient adhesion between the fluororesin and the metal conductor (metal substrate) and to obtain a sufficient peel strength (peel strength).
As a means for increasing the peel strength, for example, there is a method of bonding a metal conductor (metal substrate) and a dielectric layer via a primer or an adhesive. Primers and adhesives generally have a higher dielectric constant than dielectric layers. Therefore, there is a tendency that the transmission speed is reduced and the transmission delay and transmission loss cannot be reduced sufficiently.
As another means, there is a method in which the surface of a metal substrate is roughened in advance by etching or the like, and the peel strength is increased by utilizing the anchor effect on the rough surface. Since the metal base material flows at the surface portion of the conductor due to the skin effect at a high frequency at a high frequency, when roughened, the propagation distance tends to be long and transmission delay tends to occur. Also, resistance attenuation and leakage attenuation are large, and transmission loss tends to increase.
The fluororesin can be firmly adhered to the metal substrate by irradiating the fluororesin with ionizing radiation such as an electron beam (electron beam irradiation method).
By irradiating the fluororesin with ionizing radiation and crosslinking it, a chemical bond is also formed between the carbon atom of the fluororesin and the metal atom of the metal substrate. Therefore, the fluororesin and the metal substrate can be sufficiently brought into close contact with each other, and high peel strength can be obtained. Moreover, sufficient abrasion resistance can be obtained by crosslinking.
As a method for firmly attaching the fluororesin to the metal substrate, a method of irradiating ionizing radiation such as an electron beam is preferable. The irradiation dose of ionizing radiation is preferably an irradiation dose with which the ionizing radiation can reach the metal substrate, specifically 0.01 kGy to 500 kGy.
Irradiation with ionizing radiation is not essential, and adhesion can be achieved by laminating a fluororesin and a metal substrate and pressing them at an appropriate temperature and pressure.
The peel strength can be adjusted by controlling the irradiation conditions when the fluororesin is irradiated with an electron beam.
Polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), ethylene as low dielectric constant and low dielectric loss tangent materials -It is preferable to use a fluororesin such as tetrafluoroethylene copolymer (ETFE) or polyvinylidene fluoride (PVdF). A high-frequency circuit board in which a dielectric layer made of a fluororesin is formed on a base material (conductor) can be produced.
Since the metal base material flows at the surface portion of the conductor due to the skin effect at a high frequency at a high frequency, when it is roughened, the propagation distance becomes long and a transmission delay occurs. In addition, resistance attenuation and leakage attenuation are large, which may increase transmission loss.
A fluororesin such as polytetrafluoroethylene (PTFE) is a material having a low relative dielectric constant and a low dielectric loss tangent, and is preferable as a dielectric layer of a high-frequency circuit board. A high-frequency circuit board in which transmission delay and transmission loss are sufficiently reduced can be obtained. Moreover, a fluororesin is also preferable when producing a flexible circuit board (FPC).
These fluororesins are preferable from the viewpoint of excellent heat resistance, and are also preferable from the viewpoint that the impedance of the circuit board is less affected by humidity and is stable because of low moisture permeability.
Liquid crystal polymer (LCP) (LCP adhesive)
LCP can be preferably used for printed circuit board mounting. The LCP that has been formed into a film can be preferably used as an electronic circuit board material corresponding to thinning or high frequency.
Polycondensate of ethylene terephthalate and parahydroxybenzoic acid (Type I)

Polycondensates of phenol and phthalic acid with parahydroxybenzoic acid (Type II)
(Examples of common 4,4-dihydroxybiphenol and terephthalic acid)

Polycondensate of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Type III)

LCP is advantageous when manufacturing a high-frequency circuit board.
Thermoplastic Resins such as Acrylic Adhesives Thermoplastic resins such as acrylic adhesives (having a high glass transition temperature (Tg)) function as adhesives because their viscosity decreases upon heating.
Adhesive effect
Adhesion (peel strength)
Since it does not form on an inactive base material, it is not limited to the kind of base material.
Molded with a resin having a small relative dielectric constant εr and dielectric loss tangent tanδ.
It is preferable to use an epoxy resin adhesive (manufactured by NAMICS, Ajinomoto Technofine).
The roughened surface can be made ultra-smooth (roughness is on the order of several tens of nanometers) because the smooth PET surface roughness is transferred.

(3-5) Adhesive layer The plating transfer film has an adhesive layer.

  In the method for producing an electroless plated product using the plating transfer film of the present invention, the adhesive layer is affixed to the substrate (non-conductive substrate) by a transfer technique such as adhesive transfer. When attaching, it is a layer which adheres a substrate and a catalyst layer.

  The adhesive layer exists between the substrate and the catalyst layer. The adhesive layer remains on the substrate side when the substrate is peeled off. Due to the adhesive layer, the catalyst layer can be satisfactorily formed on the substrate, and thereafter electroless plating can be satisfactorily performed.

  The adhesive layer is formed using an adhesive composition containing an adhesive (resin) such as an acrylic adhesive, a polystyrene adhesive, a polyamide adhesive, a silicone adhesive, a urethane adhesive, or a rubber adhesive. It is preferable. These can be used alone or can be arbitrarily combined into a resin composition.

  The adhesive layer is preferably selected in consideration of the compatibility with the binder contained in the catalyst composition constituting the catalyst layer and the adhesion to the substrate (non-conductive substrate). For example, it is more preferable to use an acrylic resin or the like.

  This adhesive composition is applied onto the substrate-release layer-catalyst layer by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, or a gravure reverse roll coating method. -It can be dried to form an adhesive layer.

  The thickness of the adhesive layer is preferably about 1 to 50 μm and more preferably about 10 to 30 μm because the catalyst layer can be satisfactorily formed (adhered) on the substrate (non-conductive substrate).

  The pressure-sensitive adhesive generally has a viscosity at room temperature even after solvent drying, and imparts fluidity to the adherend by applying pressure, and the cohesiveness against peeling becomes a holding force instead of curing. The pressure-sensitive adhesive is generally thermoplastic and is used in a room temperature process, and has a low glass transition point (Tg).

  It is preferable to use an adhesive (adhesive layer) for producing the electronic circuit.

(4) Manufacturing method of plating transfer film The plating transfer film of the present invention employs the technology of the plating transfer film, and has at least a release layer, a catalyst layer, a plating film, and an adhesive layer (or adhesive layer) on the substrate. It can manufacture by laminating in order.

The plating transfer film of the present invention is
(1) forming a release layer on the substrate,
(2) A step of applying a catalyst composition to the release layer side of the substrate and providing a catalyst layer;
(3) a step of plating the catalyst layer to form a plating film; and
(4) It can be manufactured by a manufacturing method including a step of providing an adhesive layer or an adhesive layer on the formed plating film.

  The plating film is formed by electroless plating or electroplating following electroless plating (hereinafter also referred to as “plating”).

  Through this manufacturing process, a catalyst layer and a plating film can be formed on the plating transfer film. By applying the plating transfer film to the substrate (non-conductive substrate, molded product or molded product) by transfer technology, and then exposing the catalyst layer and the plating film to the substrate by peeling, the molded product or molded product is obtained. A plating film can be formed.

  Thereby, an electroless plated product can be manufactured.

(4-1) Step of forming a release layer on the substrate (1)
A substrate having releasability is produced.

  The release composition is applied and dried on a substrate by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, a gravure reverse roll coating method, and then released. A layer can be formed (base material having releasability).

(4-2) Step (2) of applying the catalyst composition to the release layer side of the substrate and providing the catalyst layer
A catalyst layer is provided on a substrate having releasability (release layer side).

The method of apply | coating a catalyst composition to the peeling layer side of the base material which has a coating process mold release property is not limited.

  Examples of the coating method include a coating method using a bar coater, a gravure printing machine (gravure offset), a flexographic printing machine, an ink jet printing machine, dipping, spraying, a spin coater, a roll coater, a reverse coater, a screen printing machine, and the like. Gravure offset printing and pad printing are preferable from the viewpoint of masking-less and production efficiency. Depending on the pattern, spray coating is preferred.

  It is preferable to adjust the viscosity of the catalyst composition in accordance with the coating method.

  When applied by gravure offset printing or pad printing, the viscosity of the catalyst composition is preferably about 50 to 1,000 mPa · s. When spray coating is performed after masking, the viscosity of the catalyst composition is preferably about 100 mPa · s or less.

  The film thickness of the catalyst composition before drying and curing can be appropriately selected depending on the intended use, and depends on the viscosity of the catalyst composition. The film thickness is preferably about 1 to 120 μm from the viewpoint of satisfactorily applying the catalyst composition. When the film thickness exceeds 120 μm, the catalyst composition tends to cause dripping.

After applying the catalyst composition to the curing treatment substrate, the solvent (solvent) contained in the catalyst composition is volatilized and / or dried, and then the curing treatment is performed. The binder is cured by the curing process.

After apply | coating a catalyst composition to a base material, a drying process can be performed. The drying treatment can efficiently remove an unnecessary solvent when performing electroless plating, and can improve the adhesion between the coating film and the substrate and the surface strength of the coating film. The temperature for the drying treatment is preferably about 60 to 400 ° C, more preferably about 80 to 150 ° C.
The time for the drying treatment is preferably about 6 seconds to 60 minutes, more preferably about 10 minutes to 30 minutes, in accordance with the drying temperature.

  The temperature of the curing treatment can be adjusted according to the type of the (3) binder contained in the catalyst composition. The temperature of the curing treatment is preferably about 40 to 400 ° C. Moreover, when using a plastic as a base material, it is preferable to set the temperature of a hardening process to about 40-200 degreeC in consideration of the softening temperature of a plastic raw material.

  The film thickness of the catalyst composition after drying and curing depends on the solid content concentration of the catalyst composition. The film thickness is preferably about 0.05 to 20 μm from the viewpoint that electroless plating can be efficiently performed and sufficient plating adhesion is exhibited. Even if the film thickness is less than 0.05 μm, the electroless plating reactivity can be obtained, but the plating adhesion tends not to be sufficiently exhibited. When the film thickness exceeds 20 μm, the reaction rate of electroless plating tends to be inferior.

  The solvent contained in the catalyst composition is volatilized and / or dried, and the binder contained in the catalyst composition is cured.

  A catalyst layer (catalyst film) can be formed on the substrate by performing a series of treatments using the catalyst composition of the present invention. The catalyst layer includes a metal complex (Pd complex or the like). A metal complex (Pd complex etc.) exists in the state uniformly disperse | distributed with respect to the coating film. Therefore, electroless plating can be performed more efficiently on the catalyst film.

(4-3) Plating the catalyst layer to form a plating film (3)
The plating is electroless plating or electrolytic plating subsequent to electroless plating (hereinafter, also referred to as “plating”).

  Pattern plating can be formed on the base material by performing electroless plating on the base material (base material sheet constituting the plating transfer film) on which the catalyst layer (catalyst film) is formed. The base material on which the catalyst layer is formed comes into contact with a plating solution for depositing a metal, thereby forming an electroless plating film.

  The catalyst layer formed of the catalyst composition on the substrate has good electroless plating reactivity, and the obtained electroless plating film has no unevenness and excellent adhesion and appearance. This is a non-conductive substrate (molded product), and is a plating film that has no unevenness and excellent appearance.

  The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. For example, copper, gold, silver, nickel or the like is preferably used as the plating solution. As the plating solution, it is preferable to use a plating solution containing copper or nickel from the relationship with the catalyst layer (catalyst film) formed of the catalyst composition.

The plating conditions can follow a conventional method. Since the catalyst layer (catalyst film) has very good electroless plating reactivity, it is not necessary to increase the reducing agent concentration or alkali component concentration of the plating solution. Therefore, not only the life of the plating solution is prolonged, but the plating is selectively deposited according to the pattern of the catalyst layer.
That is, the catalyst (catalyst film) formed from the catalyst composition (plating transfer film) is excellent in pattern forming ability.

  When an electroless copper (Cu) plating bath is used in the electroless plating treatment, the treatment temperature is preferably about 25 to 65 ° C., and the treatment time is preferably about 10 to 20 minutes. By this electroless plating treatment, a deposited film thickness of about 0.3 to 1.0 μm can be formed.

  When an electroless nickel boron (Ni-B) bath is used in the electroless plating treatment, the treatment temperature is preferably about 55 to 70 ° C., and the deposition rate is preferably about 5 μm / hr (60 ° C.).

  When an electroless nickel phosphorus (Ni-P) bath is used in the electroless plating treatment, the treatment temperature is preferably about 30 to 95 ° C., and the deposition rate is about 3 μm / hr at a bath temperature of 30 ° C. and at 90 ° C. Is preferably about 20 μm / hr.

  The technique for forming plating on the catalyst composition formed on the substrate may use the catalyst composition for whole-surface plating, and may be used for pattern plating.

  For decoration purposes, use general processes such as electrolytic copper (Cu) plating, semi-bright nickel (Ni) plating, bright nickel (Ni) plating, and chromium (Cr) plating after electroless plating. Is preferred.

When an electrolytic copper (Cu) plating bath is used in the decorating treatment, the treatment temperature is preferably about 20 to 60 ° C. Current density is preferably about 1 to 10 A / m ^2. The treatment time is preferably about 10 to 60 minutes. By a decorating process using an electrolytic Cu plating bath, a deposited film thickness of about 5 to 40 μm can be formed.

When a semi-bright nickel (Ni) plating bath is used in the decorating treatment, the treatment temperature is preferably about 45 to 55 ° C. Current density is preferably about 1 to 10 A / m ^2. The treatment time is preferably about 10 to 60 minutes. By the decorating process using a semi-bright Ni plating bath, a deposited film thickness of about 5 to 20 μm is obtained.

When a bright nickel (Ni) plating bath is used in the decorating treatment, the treatment temperature is preferably about 45 to 55 ° C. Current density is preferably about 1 to 10 A / m ^2. The treatment time is preferably about 10 to 60 minutes. By the decorating process using a bright Ni plating bath, a deposited film thickness of about 5 to 20 μm is obtained.

When a chromium (Cr) plating bath is used in the decoration treatment, the treatment temperature is preferably about 40 to 60 ° C. Current density is preferably about 10~60A / m ^2. The treatment time is preferably about 1 to 5 minutes. By the decorating process using a Cr plating bath, a deposited film thickness of about 0.1 to 0.3 μm is obtained.

  Electroless plating is performed on the substrate (substrate sheet constituting the plating transfer film) on which the catalyst layer (catalyst film) is formed, and then pattern plating is formed on the substrate by performing electrolytic plating. be able to.

(4-4) Step of providing an adhesive layer or adhesive layer on the formed plating film (4)
An adhesive layer or an adhesive layer is provided on the catalyst layer.

  The adhesive composition or the pressure-sensitive adhesive composition can be released from a substrate having releasability by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, or a gravure reverse roll coating method ( The adhesive layer or the pressure-sensitive adhesive layer can be formed by applying and drying on the base material-peeling layer) -catalyst layer.

(5) Method for producing a plated product Using the plating transfer film of the present invention, a smooth plating film (electroless plating film or electrolytic plating film) can be formed on a non-conductive substrate.

To produce a plated product using a transfer film,
(1) A process of attaching an adhesive layer or an adhesive layer of a plating transfer film to a substrate, and
(2) A method including a step of leaving a catalyst layer, a plating film, and an adhesive layer or an adhesive layer of a plating transfer film on the substrate, and peeling the substrate from the substrate with respect to the paste obtained by the step Thus, a plated product can be manufactured.

  Steps (1) and (2) employ in-mold transfer, hot roll transfer, or adhesive transfer transfer techniques.

(5-1) Transfer technology (Figures 1-3)
The transfer technique is mainly a hot roll transfer technique, an in-mold transfer technique, or an adhesive transfer. Using the transfer technique, the catalyst layer and the plating film of the plating transfer film can be attached to a non-conductive substrate (molded product) to decorate the non-conductive substrate (molded product).
In the manufacture of printed wiring boards for electronic devices, metal wiring circuits can be formed.
The transfer technique of the present invention is an advantageous technique particularly when producing a high-frequency circuit board used in a high-frequency communication device, particularly a flexible circuit board (flexible printed circuit: FPC).
Using the plating transfer film transfer film of the present invention, the catalyst layer and the plating film are pattern-formed (exposed) on the wiring board (non-conductive substrate).

(5-1-1) Thermal roll transfer technology (Figures 1 and 3)
The molded product (molded product) is preferably molded (molded) by a hot roll transfer technique using a plating transfer film.

  The hot roll transfer technology includes (1) a step of preparing the plating transfer film of the present invention, (2) a step of installing the plating transfer film on a molded (molded) resin body, and (3) heat pressure while being installed. It is preferable to include a roll transfer step.

  The hot roll transfer technique preferably includes the following steps (i) to (iii).

  (i) Press the adhesive layer of the plating transfer film against the non-conductive substrate (molded product) using a heated roller (rubber roller, silicon roller, etc.).

  (ii) The adhesive layer of the plating transfer film is melted by heat and pressure, and the adhesive layer is adhered to the surface of the non-conductive substrate.

  (iii) The substrate (including the release layer) having releasability of the plating transfer film is peeled off, and the catalyst layer and the plating film are transferred (formed) to the non-conductive substrate to expose the plating film.

  The hot roll transfer technique is a technique for transferring the catalyst layer and the plating film on the substrate of the plating transfer film to the surface of the non-conductive substrate by applying heat and pressure with a heated roller.

  Furthermore, it is possible to upgrade the design by partial aluminum vapor deposition, mat printing, etc., or to add functionality such as a hard coat. It is possible to plate (decorate) a pattern or the like on the non-conductive substrate, that is, to give a design. It can be used in fields such as household goods, household appliances, and cosmetics.

  In the hot roll transfer process, the plating transfer film can be transferred by a printing method such as rotogravure or rotatory silk screen.

With the heat roll transfer technology of the present invention, it is easy to paint multi-colored / photo-decomposed patterns that are difficult to print directly on molded products. Simultaneous processing of further surface treatment such as hard coat is possible. A metal feeling can be expressed on the surface by using vapor deposition.
Since no solvent or the like is used during transfer processing, the working environment can be improved. Equipment can be simplified and productivity can be improved. Flexible response to various materials is possible.

  In the thermal roll transfer technology, designs (plating) such as patterns, metal tones, pearls, matte tones are applied from the surface of non-conductive base materials (molded products) such as plastics to the surface of cubic surfaces such as cylinders. You can do (decorate).

  Compared with printing, painting, and other technologies for molded products, the hot roll transfer technology is a decorative method with less environmental impact due to organic solvents. The hot roll transfer technology makes it easy to paint multicolored and photo-separated patterns that are difficult to print directly on molded products. Since no solvent or the like is used during transfer processing, the working environment can be improved. Equipment can be simplified and productivity can be improved. Flexible response to various materials is possible.

The thermal roll transfer technology can be applied to household goods, stationery, cosmetics, home appliances, metal wiring circuits, and the like.
The heat roll transfer technology of the present invention includes, for example, communication devices such as mobile phones; low-power devices such as refrigerators, fluorescent lights, switch panels; automobile parts such as fan belts and indicators; lunch boxes, cups, chopsticks, stainless steel bottles, trash cans Household goods such as toiletries, bath goods, storage goods, writing instruments (pencils, mechanical pencils, etc.), rulers, pencil caps, stationery and toys such as video games, cosmetics such as containers, tubes, bottles, caps, ski boots, It can be applied to sporting goods such as ski stocks, skis, golf clubs, etc .; metal wiring circuits.

(5-1-2) In-mold transfer technology (Figures 2 and 3)
The molded product (molded product) is preferably molded (molded) by using an in-mold transfer technique (injection molding simultaneous transfer method) using a plating transfer film.

  In-mold transfer technology consists of (1) the process of preparing the plating transfer film of the present invention, (2) the process of inserting the plating transfer film into the mold for in-mold molding, and (3) the melting in the mold. It is preferable to include a step of injecting and injecting the injected resin, and (4) integrating the plating transfer film and the injection resin to form a catalyst layer on the surface of the resin molding.

  The in-mold transfer technique preferably includes the following steps (i) to (iv).

  (i) The plating transfer film is supplied from the foil feeder into the mold, and the plating transfer film is positioned using a camera, a sensor, or the like.

  (ii) The plating transfer film is fixed by clamping and suction, and the mold is clamped.

  (iii) The plating film (adhesive layer) is transferred to the non-conductive substrate (molded product) in the mold by the resin temperature and the injection pressure.

  (iv) Simultaneously with mold opening, the plating transfer film is peeled off from the substrate (including the release layer) having the releasability, and the catalyst layer and the plating film are transferred (formed) to the non-conductive substrate. To expose. The molded product (finished product) is taken out automatically or manually.

  In-mold transfer technology sends a plating transfer film into a mold and, at the time of molding, creates a molded product using the heat and pressure that is inherent, and at the same time, the surface of the molded product on the substrate of the plating transfer film This is a technology for transferring the catalyst layer.

The in-mold transfer technique of the present invention enables plating (decoration) on a non-conductive substrate on a three-dimensional curved surface, a perforated molded product, and a gentle uneven surface, which has been impossible in the past. Combining with a functional material such as a hard coat can increase the added value of the product. Costs can be reduced by simplifying the process. Energy saving and space saving can be achieved, which leads to improvement of working environment. Excellent position accuracy of the pattern with respect to the molded product.
The in-mold transfer technique can form a plating film on the surface of a molded product having a cubic curved surface at the same time that a non-conductive substrate such as plastic is molded in a mold. Various highly designable designs (plating) can be applied (decorated) with high positional accuracy on the surface of the cubic surface of the non-conductive substrate (molded product). The in-mold transfer technology is excellent in the positional accuracy of the pattern with respect to the molded product.

  In-mold transfer technology is a decorative method that reduces the environmental impact of organic solvents, and can save space and reduce costs. Three-dimensional curved surfaces, perforated molded products, and gentle uneven surfaces, which were previously impossible. Plating (decoration) is possible.

The in-mold transfer technology of the present invention can be applied to, for example, communication equipment, light electrical equipment, automobile parts, household goods, leisure goods, metal wiring circuits, and the like.
The in-mold transfer technology of the present invention includes, for example, communication devices such as mobile phones; low-power devices such as refrigerators, air conditioners, personal computers, and audio; automobile parts such as indicators and car air conditioners; household items such as lunch boxes, key chains, and nail clippers. It can be applied to leisure goods such as pachinko nameplates and metal wiring circuits.

(5-1-3) Adhesive transfer technology (Figure 3)
The plating transfer film of the present invention is formed by laminating at least a catalyst layer, a plating film, and an adhesive layer in this order on a releasable base material (including the release layer 1), and further to the adhesive layer, the release layer 2 May be laminated.

  The molded product (molded product) is preferably molded (molded) using an adhesive transfer technique using a plating transfer film. The pressure-sensitive adhesive transfer technique preferably includes (1) a step of preparing the plating transfer film of the present invention, and (2) a step of attaching the pressure-sensitive adhesive side of the plating transfer film on the molded (molded) resin body. .

  The pressure-sensitive adhesive transfer technique preferably includes the following steps (i) to (iii).

  (i) Press the adhesive layer of the plating transfer film against the non-conductive substrate (molded product). When the release layer 2 is laminated on the adhesive layer of the plating transfer film, the release layer 2 is peeled off, and then the adhesive layer of the plating transfer film is pressed against the non-conductive substrate.

  (ii) Adhering the adhesive layer of the plating transfer film to the surface of the non-conductive substrate.

  (iii) The substrate (including the release layer 1) of the plating transfer film is peeled off, and the catalyst layer and the plating film are transferred (formed) to the non-conductive substrate to expose the plating film.

The pressure-sensitive adhesive transfer technique is a technique in which the catalyst layer and the plating film on the substrate of the plating transfer film are directly and simply transferred to the surface of the non-conductive substrate with the pressure-sensitive adhesive. It is possible to plate (decorate) a pattern or the like on the non-conductive substrate, that is, to give a design.
Furthermore, it is possible to upgrade the design by partial aluminum vapor deposition, mat printing, etc., or to add functionality such as a hard coat.

  Adhesive transfer technology forms a pattern on the surface of a third-order curved surface, such as a cylindrical object, from a flat surface of a non-conductive substrate (molded product) such as plastic. Design (plating) such as pearl and matte can be imparted (decorated). Compared to printing, painting, and other technologies for molded products, the adhesive transfer technology is a decorative method with less environmental impact due to organic solvents.

  The pressure-sensitive adhesive transfer technology of the present invention makes it easy to paint multi-colored / photo-decomposed patterns that are difficult to print directly on molded products. Simultaneous processing of further surface treatment such as hard coat is possible. A metal feeling can be expressed on the surface by using vapor deposition. Since no solvent or the like is used during transfer processing, the working environment can be improved. Equipment can be simplified and productivity can be improved. Flexible response to various materials is possible.

  Since no solvent or the like is used during transfer processing, the working environment can be improved. Equipment can be simplified and productivity can be improved. Flexible response to various materials is possible.

The adhesive transfer technology can be applied to communication equipment, light electrical equipment, automobile parts, household goods, stationery / toys, cosmetic containers, sports equipment, metal wiring circuits, and the like.
Adhesive transfer technology of the present invention includes, for example, communication devices such as mobile phones; low-power devices such as refrigerators, fluorescent lights and switch panels; automobile parts such as fan belts and indicators; lunch boxes, cups, chopsticks, stainless steel bottles, and trash cans. Household goods such as toiletries, bath goods, storage goods, writing instruments (pencils, mechanical pencils, etc.), rulers, pencil caps, stationery and toys such as video games, cosmetics such as containers, tubes, bottles, caps, ski boots, It can be applied to sporting goods such as ski stocks, skis, golf clubs, etc .; metal wiring circuits.

  In the production of printed wiring boards for electronic devices, the catalyst layer catalyst layer is formed on the wiring board (non-conductive substrate) using the plating transfer film of the present invention by the hot roll transfer technique, the in-mold transfer technique or the adhesive transfer technique In addition, a metal wiring circuit can be formed by patterning (exposing) the plating film.

(5-2) Step of attaching the adhesive layer or adhesive layer of the plating transfer film to the substrate (1)
The adhesive layer or adhesive layer of the plating transfer film is attached to the substrate by a transfer technology such as a hot roll transfer technology, an in-mold transfer technology, or an adhesive transfer.

It is an object to which a plating film is transferred by a base plating transfer film.

  The substrate is not particularly limited. The substrate is preferably a non-conductive substrate such as plastic.

  As the substrate, it is preferable to use plastic (resin), glass, ceramics or the like.

  As the plastic, it is preferable to use polyolefin such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, and polyisoprene.

  As the plastic, it is preferable to use an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) or the like.

Polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid ester; acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate (PC); polyvinyl chloride; polyamide; polyimide; It is preferable to use ether imide; polyacetal;
Further, it is preferable to use polyether ether ketone; cyclic polyolefin having norbornene skeleton; polyphenylene sulfide; liquid crystal polymer; modified polyphenyl ether; polysulfone; phenol; polyphthalamide (PPA);

  Examples of ceramics include glass and alumina. Moreover, when using a nonwoven fabric as a base material, nonwoven fabrics, such as a wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber, are mentioned.

  Use of a thermoplastic resin or thermosetting resin (including a two-component curable resin) that can be molded (molded) as an injection resin used in manufacturing by injection molding (molding) such as in-mold molding (molding). Is preferred.

When a thermoplastic resin is used as the injection resin, polystyrene (PS), polyolefin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer (copolymerization compound) (AS resin), polyphenylene oxide, It is preferable to use a resin such as polycarbonate (PC) or polyacetal (POM).
As the injection resin, it is preferable to use a resin such as acrylic resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polysulfone, or polyphenylene sulfide.

  When a thermosetting resin is used as the injection resin, it is preferable to use a two-component curable urethane resin, an epoxy resin, or the like.

  As the injection resin, the resin may be used alone, or two or more kinds may be mixed and used.

  The shape of the substrate is not particularly limited. For example, it may be any of a plate shape (or film shape), a nonwoven fabric shape (or woven fabric shape), a thread shape, various shapes formed by a mold, and the like.

  Depending on the substrate (non-conductive substrate), a solvent, a binder and the like contained in the catalyst composition (catalyst layer of the transfer film) can be appropriately selected.

When the plating transfer film of the present invention is used, a plating film (such as a conductive circuit) can be satisfactorily formed even on a substrate that cannot or cannot withstand a plating bath by a transfer technique.
The transfer technique of the present invention is an advantageous technique particularly when producing a high-frequency circuit board used in a high-frequency communication device, particularly a flexible circuit board (flexible printed circuit: FPC).

  As a substrate, it is possible to transfer the plating film to paper, cloth or the like. These papers, cloths and the like are usually substrates that cannot or cannot withstand a plating bath because of their characteristics.

(5-3) Step (2) for removing the substrate from the substrate, leaving a catalyst layer, a plating film, and an adhesive layer or an adhesive layer of the plating transfer film on the substrate, for the obtained paste.
In in-mold transfer (simultaneous injection molding transfer method), after the resin molded body is cooled and taken out from the mold, the substrate (base material sheet, peeled portion) having the releasability of the plating transfer film is peeled off. By doing so, a molded product with the catalyst layer exposed can be obtained.

  In the hot roll transfer method, a molded product with the catalyst layer exposed can be obtained by further peeling the substrate (base material sheet, peeled portion) having releasability of the plating transfer film.

  In the pressure-sensitive adhesive transfer method, a molded product with the catalyst layer exposed can be obtained by further peeling the substrate (base sheet, peeled portion) having releasability of the plating transfer film.

(6) Molded product with plating film (plated product)
The plating transfer film of the present invention is applied to a substrate (non-conductive substrate, plastic (resin), etc.) to form a plating film. Thereby, the plating film by which pattern plating or partial plating was carried out can be formed. A molded product (plating object) on which a plating film is placed has excellent adhesion of the plating film.

  The molded product on which the plating film is placed can be used for, for example, a housing of an electric appliance such as a mobile phone, a personal computer, and a refrigerator; an automobile part such as an emblem, a switch base, a radiator grill, a door handle, and a wheel cover. .

  With the plating transfer film of the present invention, the plating (especially electroless plating) is highly reactive in pattern plating on the substrate, excellent adhesion with chrome plating, and excellent smoothness of decorative plating Can be expressed. In the plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

  When the plating transfer film of the present invention is used, it is not necessary to increase the concentration of the reducing agent in electroless plating and to increase the reaction temperature of electroless plating for the purpose of improving the electroless plating reactivity. Furthermore, there is no need for an etching step with a harmful substance, a complicated catalyst application step, or the like.

In the in-mold transfer method or the hot roll transfer method, the adhesive layer (adhesive) of the transfer film is melted by heat at the time of thermal transfer, and the substrate and the adhesive layer are in close contact with each other.
FIG. 7 shows a circuit formation method by the metalloid method.
(1) in FIG. 7 is a conventional subtractive method.
First, copper foil is laminated to FR-4 (glass epoxy substrate) using an epoxy adhesive. This is a method for forming a desired electronic circuit by photolithography technology.
(2) in FIG. 7 is a conventional semi-additive method.
This method can form a fine pattern circuit. First, there is a method in which a catalyst is applied to the entire surface, and subsequently, by using a photolithographic technique, circuit pattern formation, plating, resist removal, and catalyst residue removal are performed to form a target electronic circuit.
FIG. 7 (3) shows a circuit formation method by the metalloid method of the present invention.
This method is a method of forming a desired electronic circuit by electroless plating and electroplating by pattern printing of an electroless plating catalyst (metalloid) using various printing techniques.
This method has an advantage that a large amount of copper waste liquid discharged in the etching process and the resist material required in the subtractive method or the semi-additive method is not necessary.
FIG. 8 shows a method for producing a high-frequency double-sided flexible substrate by the metalloid transfer system of the present invention.
(1) in FIG. 8 shows a method for producing a metalloid transfer film (ML-TRF).
First, an electroless plating catalyst (metalloid) is pattern-printed on the release film using various printing techniques. Thereafter, a metalloid transfer film (ML-TRF) can be produced through a low-loss varnish coating process such as an epoxy material.
This film should be stored refrigerated in a semi-cured (B stage) state. The surface of the substrate after the metalloid transfer is smooth, which is advantageous for high frequency circuit applications.
(2) in FIG. 8 shows a method for producing a high-frequency double-sided flexible substrate by a metalloid transfer method.
Metalloid transfer film (ML-TRF) is thermally transferred to both sides of the support substrate such as FR-4 (glass epoxy), PI, PET, aluminum foil by a vacuum press method so that the upper and lower electrode positions are accurate. Thereafter, the release film is removed, and the target electronic circuit is formed on the exposed metalloid pattern portion by electroless electroplating. Thereafter, the electrodes on both sides are connected.
As a connection method, first, a through hole (through hole) is provided by a drill or a laser. Thereafter, hole filling is performed with a conductive paste to connect the double-sided electrodes. Finally, for the purpose of circuit protection, a coverlay (protective film) is laminated to produce a high-frequency double-sided flexible substrate.
By this method, a large amount of copper waste liquid discharged in the resist material and the etching process becomes unnecessary.
FIG. 9 shows a method for producing a high-frequency substrate by the plating transfer method of the present invention.
(1) in FIG. 9 shows a method for producing a plating transfer film (ML-MTRF).
(2) in FIG. 9 shows various chip component mounting plating transfer films.
First, an electroless plating catalyst (metalloid) is pattern-printed on the release film using various printing techniques. Thereafter, a target electronic circuit can be formed by electroless plating and electroplating to produce a plating transfer film (ML-MTRF). Furthermore, various chip components whose mounting positions are determined are fixed on the transfer substrate using an adhesive or a double-sided tape.
By connecting the chip component electrode and the transfer plating pattern electrode with a conductive material such as conductive paste and ink, various chip component mounting plating transfer films can be produced.
FIG. 10 shows a method for producing a high-frequency substrate by the plating transfer method of the present invention.
(1) in FIG. 10 shows a method for producing a high-frequency flexible substrate by a plating transfer method.
(2) in FIG. 10 shows a method for producing a chip component built-in high-frequency flexible substrate using various metal plating transfer films mounted with chip components.
A plating transfer film (ML-TRF) or a chip component mounting metal plating transfer film and a low-loss material coated film are vacuum hot pressed. Thereafter, the release film is removed.
If the low-loss material is cured during the thermal transfer process and loses its adhesiveness, it should be further adhered to a substrate such as FR-4 (glass epoxy), PI, PET, or aluminum foil using a film adhesive. Thus, a high-frequency flexible substrate or a high-frequency flexible substrate incorporating various chip components can be manufactured.
In the case of in-mold transfer molding, it is possible to produce a substrate-less high-frequency substrate that is flat or cylindrical, such as a cylindrical object, or a high-frequency substrate with built-in various chip components.
By this method, the electronic circuit is molded into a low-loss material, which is advantageous for high-frequency substrate applications. By using a substrate with good heat dissipation characteristics, a high-frequency substrate with good heat dissipation characteristics can be manufactured. In addition, parts manufacturers do not require a plating process, and the required amount of production can be produced by an all-dry process.
FIG. 11 shows (1) high frequency substrate, (2) ML-MTRF, and (3) skin depth (calculated value) for each metal frequency of the present invention.
(3) in FIG. 11 shows the skin depth (calculated value) for each metal frequency.
In the high-frequency region exceeding 30 GHz, the copper thickness of 1 μm or less is sufficient for calculation, and the surface roughness of the newly developed high-frequency substrate is as smooth as 30 NM or less, and the loss due to the surface roughness can be ignored.
Application example Millimeter wave radar (76 GHz) Circuit board Quasi-millimeter wave radar (24 GHz)
Car rear-end collision prevention, guerrilla heavy rain monitoring, illegal dumping monitoring, wireless LAN

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

  A catalyst composition for a transfer film for electroless plating is referred to as a catalyst composition.

  A transfer film for electroless plating is referred to as a transfer film.

  “Weight%” is also described as “wt%”.

[1] Preparation of complex of palladium particles (Pd particles) and dispersant (Pd colloid)
1 part by weight of Pd chloride (Pd compound) was dissolved in 89 parts by weight (dispersion solvent) of purified metal nanoparticles by a liquid phase reduction method , and further 10 parts by weight of trisodium citrate was dissolved and stirred uniformly. Next, 0.01 part by weight of sodium borohydride was added to reduce Pd chloride and stabilized with citric acid to obtain a protective colloid Pd colloid.

  Subsequently, concentration desalting was performed by ultrafiltration to obtain a Pd colloid containing 0.5 part by weight of Pd.

[2] Example (Preparation of plating transfer film)
(1) Ink
(A) Examples 1 and 10
Pd complex-containing liquid (Pd content 12.75 wt%, manufactured by Iox Corporation): 1.96 g, PVC-vinyl acetate resin (solid content 10 wt%, manufactured by DIC Graphics): 9.0 g, and cyclohexane / MIBK / MEK mixed A solvent (solvent) was mixed so that the Pd concentration was 5,000 ppm (0.5 wt%) to prepare a metal plating transfer film catalyst composition (ink).

(B) Examples 2-5
Pd complex-containing liquid (Pd content 12.55 wt%, manufactured by Iox Corporation): 1.96 g, PVC-vinyl acetate resin (solid content 40 wt% (toluene / MIBK diluted, manufactured by Nissin Chemical)): 2.5 g, and terpineol / NMP mixed solvent (solvent) was mixed so that the Pd concentration was 10,000 ppm (1 wt%) to prepare a metal plating transfer film catalyst composition (ink).

(C) Examples 6-9
Pd complex-containing liquid (Pd content 12.75 wt%, manufactured by Iox Corporation): 0.1 g, Byron 24SS (polyester resin, solid content 10 wt%, manufactured by Toyobo Co., Ltd.): 0.3 g (binder), and cyclohexane / MIBK / A MEK mixed solvent (solvent) was mixed so that the Pd concentration was 5,000 ppm (0.5 wt%) to prepare a metal plating transfer film catalyst composition (ink).

(2) Formation of catalyst layer forming film for metal plating transfer
(A) Examples 1 and 6-9
Bar coater # 4 (coating thickness: 4 μm) on the release layer of the non-silicon release polyethylene terephthalate (PET: 38 μm) (transfer film substrate + release layer). And then dried at 120 ° C. for 1 minute in a drying oven.

(B) Examples 2-5
The obtained electroless plating transfer film catalyst composition is printed on a release layer of non-silicone release polyethylene terephthalate (PET: 38 μm) (transfer film substrate + release layer) by an offset printing method. (FIG. 5) was used for printing.

  The pattern plate has a line width of 1000 μm, 500 μm, 400 μm, a pitch, and a depth of 30 μm. Subsequently, it was dried in a drying oven at 120 ° C. for 1 minute.

(C) Example 10
The obtained electroless plating transfer film catalyst composition is printed on a release layer of non-silicon release polyethylene terephthalate (PET: 38 μm) (transfer film substrate + release layer) using a gravure printing machine. Roll-to-roll continuous printing was performed using a plate (FIG. 6). The gravure pattern plate used 300 lines, 10 μm depth, 65 ° angle, and 200 μm line width.

(3) Metal plating layer formation
(A) Examples 1 to 5
The obtained catalyst-coated film was subjected to electroless plating.

  As the electroless copper plating bath, OPC Copper HFS (initial Cu concentration 2.5 g / l, bath volume 500 ml, 40 ° C., 40 minutes) manufactured by Okuno Pharmaceutical Co., Ltd. was used. The thickness of the metal plating on the obtained metal plating transfer film was 2 μm.

(B) Examples 6-9
The obtained catalyst-coated film was subjected to electroless plating.

  Electroless plating was performed for 10 minutes. As the electroless nickel plating bath, BEL18 (initial Ni concentration 6 g / l, bath volume 500 ml, 65 ° C.) manufactured by Uemura Kogyo Co., Ltd. was used. The thickness of the metal plating on the obtained metal plating transfer film was 1 μm.

(C) Example 10
The obtained catalyst-coated film was electrolessly and electroplated.

  As the electroless copper plating bath, OPC Copper HFS (initial Cu concentration 2.5 g / l, bath volume 500 ml, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Co., Ltd. was used. The electrolytic copper plating bath used was a copper sulfate concentration of 80 g / L and a sulfuric acid concentration of 150 g / L. The thickness after plating was 13 μm.

(4) Thermal transfer (thermal roll transfer)
(A) Examples 1 (solid printing) and 2 (pattern printing)
Apply an epoxy adhesive (solid content 22%, manufactured by Toa Gosei Co., Ltd.) to the electroless plating surface of the metal plating transfer film using a bar coater # 22 (coating thickness: 22 μm), and then in a drying oven It was dried at 120 ° C. for 1 minute.

  Furthermore, acrylic medium (solid 20 wt%, manufactured by Dainichi Seika Kogyo Co., Ltd.) was applied onto the adhesive coated surface using a bar coater # 22 (coating thickness: 22 μm), and then in a drying oven. It was dried at 120 ° C. for 1 minute.

  After that, using a thermal transfer device (Naitas RT-300 manufactured by Taihei Kogyo Co., Ltd.), it was thermally transferred to a flat acrylic plate (thickness: 2 mm, vertical and horizontal: 50 mm) at a temperature of 220 ° C., a pressure scale of 110, and three times pressing. .

(5) Adhesive transfer
(A) Examples 3 to 7 and 10 (Examples 6 and 7: solid printing)
Apply an epoxy adhesive (solid content 22%, manufactured by Toa Gosei Co., Ltd.) to the electroless plating surface of the metal plating transfer film using a bar coater # 22 (coating thickness: 22 μm), and then in a drying oven It was dried at 120 ° C. for 1 minute.

  Further, SK Dyne 1435 (adhesive, 30% solid content, manufactured by Soken Chemical Industry Co., Ltd.) was applied using a bar coater # 47 (coating thickness: 47 μm), and then dried in a drying oven at 120 ° C. for 1 minute.

Thereafter, the image was transferred onto copy paper (64 g / m ² basis weight) or label sticker paper using a rubber roller.

  In the case of pattern printing, when the adhesive was applied directly, the portions other than the pattern were sticky, so an epoxy adhesive having no tack was applied in the middle.

(B) Examples 8 and 9
SK Dyne 1435 (solid content 30%, manufactured by Soken Chemical Industry Co., Ltd.) Bar Coater # 47 (coating thickness: 47 μm) was applied to the electroless plating surface of the metal plating transfer film, and then it was 120 in a drying oven. It was dried at 0 ° C. for 1 minute.

Then, it transferred to a copy paper (64 g / m ² basis weight) or a label sticker paper using a double-sided adhesive tape and a rubber roller.

(6) Conductivity measurement In Examples 3 to 9, ink was transferred to paper or cloth, and its resistance was measured. Paper or fabric is a substrate that, due to its properties, cannot withstand or face a plating bath.

(A) Examples 1, 6, 7 and 10
The surface resistance of each electroless plating or electroless, electroplating transfer substrate obtained by thermal transfer and adhesive transfer was measured using Loresta GP MCP-T610 manufactured by Mitsubishi Chemical Analytech.

The surface resistance of the electroless copper plating transfer acrylic plate obtained in Example 1 was 2.21 × 10 ⁻² / □. The resistance of the metal copper plating layer before transfer was 2.1 × 10 ⁻² / □.

  When the metal copper plating layer transfer film of this invention was used, it turned out that the antioxidant process to an oxidizing metal plating layer is unnecessary.

EXAMPLE surface resistance of electroless nickel plating transfer copy sheet and label sticker sheet obtained in 6 and 7 were respectively 3.02 × 10 ^-1 /□,3.38×10 ^-1 / □ a.

The resistance of the metallic nickel plating layer before transfer was 5.56 × 10 ⁻¹ / □.

The surface resistance of the electroless and electrolytic copper plating transfer copy paper obtained in Example 10 was 5.40 × 10 ⁻³ / □.

The resistance of the metal copper plating layer before transfer was 5.33 × 10 ⁻³ / □.

(B) Examples 2 to 5, 8 and 9 (Examples 8 and 9: solid printing)
Using a KM-320N tester manufactured by Custom Co., Ltd., the electrical resistance between the 10 μm wide plating pattern or the 10 mm electrode on the solid plating surface was measured.

[3] Summary of measurement results The surface resistance of the electroless plating transfer substrate obtained by thermal transfer, adhesive transfer, and double-sided adhesive tape transfer was plated using a KM-320N tester manufactured by Custom Co., Ltd. The electrical resistance between 10 mm electrodes on the pattern or plating film surface was measured.

  The measurement results of Examples 1 to 10 are summarized in Table 1.

  When the metal plating layer transfer film of this invention was used, it turned out that the antioxidant process to an oxidizing metal plating layer is unnecessary.

[4] Example (production of high-frequency circuit board)
A fluororesin such as PTFE is a material having a low relative dielectric constant and a low dielectric loss tangent, and is preferable as a dielectric layer of a high-frequency circuit board. Since the fluororesin has a remarkably low surface energy and is non-adhesive, an electron beam irradiation method is used to ensure sufficient adhesion with a metal conductor (metal substrate) (to obtain peel strength (peel strength)). Using.
1． An electrolytic copper foil CF-LB9 (thickness: 20 μm, surface roughness: Rz = 1.0 μm) manufactured by Fukuda Metal Foil Powder Co., Ltd. was immersed in dilute sulfuric acid to produce a copper foil from which the coating for preventing oxidation was removed. .
2． On the copper foil, a PTFE dispersion (EK-3700) manufactured by Daikin Industries, Ltd. was applied by casting and dried. Thereafter, it was baked at 360 ° C. in a nitrogen atmosphere (for preventing oxidation) to produce a 15 μm PTFE film on the copper foil.
3． Using a Nissin Electric electron beam irradiation device (acceleration voltage: 1.13 MeV), the copper foil on which the PTFE film was fabricated was irradiated with an electron beam of 300 kGy in an atmosphere with an irradiation temperature of 340 ° C and an oxygen concentration of 5 ppm. The test specimen was obtained by cross-linking PTFE and simultaneously bonding the copper foil and PTFE.
Adhesion (peel strength)
Since it does not form on an inactive base material, the kind of base material is not limited.
It can be molded with a resin having a small relative dielectric constant εr and dielectric loss tangent tanδ.
The surface roughened surface is ultra-smooth (roughness is on the order of several tens of nm) because the smooth PET surface roughness is transferred.

  Using the plating transfer film of the present invention, a plating film can be satisfactorily formed on the substrate by various transfer techniques.

  Since the plating film is formed on the transfer film, it is possible to form the plating film on the substrate at once by various transfer techniques.

By using the plating transfer film of the present invention, it is possible to easily transfer a conductive circuit to a substrate that cannot normally withstand a plating bath or a substrate that is not suitable for a plating bath by various transfer techniques. .
The present invention can provide a plating transfer film on which a plating film is formed when a high-frequency circuit board used in a high-frequency communication device, particularly a flexible circuit board (FPC), is produced. INDUSTRIAL APPLICABILITY The present invention can be used in a high frequency region, and a high frequency circuit board with a smaller transmission delay and transmission loss can be manufactured.
The plating transfer film for producing a high-frequency circuit board of the present invention can form an electroless plating film having a smooth surface. Unlike conventional metal wiring transfer, high-frequency circuits are required to have excellent smoothness and a low loss rate of the substrate material.
By applying the plating transfer film for producing a high-frequency circuit board of the present invention to “substrate-less”, chip parts can be fixed and simultaneous coating transfer can be performed at the time of metal plating transfer. In that case, the resin can be used up to ABS or the like. Parts can be embedded with general-purpose resin materials such as ABS resin and polycarbonate.
“Boardless” is a technique for connecting components by providing a wiring function to a housing or a structural component without using a printed wiring board.
By embedding and fixing the parts together at the time of injection molding of the resin parts, or forming the wiring by ink jet printing without a plate, mounting different from the existing method can be realized without increasing the number of steps. For example, an electronic component such as an IC is embedded in injection-molded resin, and wiring and connection are performed by inkjet printing of Ag nano ink.
Since it is possible to form an electronic circuit without using a printed circuit board by using the plating transfer film for creating a high-frequency circuit board according to the present invention, it contributes to downsizing of products and reduction of environmental load, For simplicity, it also has the flexibility to handle high-mix low-volume production.
When the present invention is used for high frequency, it is preferable to use an epoxy, LCP, or fluorine resin. When the present invention is applied without a substrate, various chip components are positioned and fixed simultaneously using an adhesive or double-sided tape during high-frequency circuit pattern transfer, and the transfer plating circuit and the chip electrode are connected using a conductive paste. It can be peeled after being coated with epoxy or the like and cured. The wiring is molded.

Claims (7)

A plating transfer film in which at least a catalyst layer, a plating film, and an adhesive layer are sequentially laminated on a substrate having releasability,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a catalyst composition containing a solvent and (3) a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. And
The adhesive layer is an acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy adhesive. An adhesive layer comprising at least one adhesive selected from the group consisting of fluororesin, liquid crystal polymer (LCP), polyurethane adhesive, vinyl acetate resin emulsion, EVA resin emulsion and acrylic resin emulsion,
The transfer is in-mold transfer, hot roll transfer or adhesive transfer.
Plating transfer film for creating high-frequency circuit boards.   The dispersant of the catalyst composition is at least selected from the group consisting of a polycarboxylic acid polymer dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and a block copolymer type polymer dispersant having a carboxyl group. The plating transfer film according to claim 1, which is a kind of dispersant.   The catalyst composition solvent is water; an aprotic polar solvent selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone Polar solvents; alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, 1-butyl alcohol and isobutyl alcohol; ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol and cyclohexanone; ethylene glycol Glycol ethers selected from the group consisting of monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acids selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate Sterols; aromatic hydrocarbons selected from the group consisting of toluene and xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, At least one selected from the group consisting of glycol ether esters selected from the group consisting of butyl cellosolve acetate, methyl carbitol acetate and butyl carbitol acetate; alkanol esters selected from the group consisting of ethyl acetate and butyl acetate; 2-phenoxyethanol The plating transfer film according to claim 1, which is a seed solvent.   The binder of the catalyst composition is an acetal resin, an epoxy resin, an ester resin, an acrylic resin, a urethane resin, an amide resin, an imide resin, an amideimide resin, a shellac resin, a melamine resin, a urea resin, a vinyl chloride-vinyl acetate copolymer, and an olefin. The plating transfer film according to claim 1, which is at least one binder selected from the group consisting of resins.   The substrate having releasability is melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin release agent and The plating transfer film in any one of Claims 1-4 which is a base material containing the peeling layer which consists of an at least 1 sort (s) of release agent chosen from the group which consists of an acrylic resin type release agent. A method for producing the plating transfer film according to claim 1,
(1) forming a release layer on the substrate,
(2) A step of applying a catalyst composition to the release layer side of the substrate and providing a catalyst layer;
(3) a step of plating the catalyst layer to form a plating film; and
(4) including a step of providing an adhesive layer on the formed plating film,
Manufacturing method of plating transfer film. A method for producing a plated article using the plating transfer film according to claim 1,
The plating transfer film is formed by laminating at least a catalyst layer, a plating film, and an adhesive layer in order on a substrate having releasability,
(1) a process of attaching an adhesive layer of the plating transfer film to a substrate, and
(2) For the paste obtained by the above step, leaving the catalyst layer of the plating transfer film, the plating film, and the adhesive layer on the substrate, and including the step of peeling the substrate from the substrate,
The steps (1) and (2) are performed by in-mold transfer, hot roll transfer or adhesive transfer.
A method for producing a plated product.